US20110163452A1 - Semiconductor device, method of manufacturing semiconductor device, and substrate processing apparatus - Google Patents
Semiconductor device, method of manufacturing semiconductor device, and substrate processing apparatus Download PDFInfo
- Publication number
- US20110163452A1 US20110163452A1 US12/984,018 US98401811A US2011163452A1 US 20110163452 A1 US20110163452 A1 US 20110163452A1 US 98401811 A US98401811 A US 98401811A US 2011163452 A1 US2011163452 A1 US 2011163452A1
- Authority
- US
- United States
- Prior art keywords
- film
- metal film
- metal
- chamber
- gas
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 239000000758 substrate Substances 0.000 title claims abstract description 79
- 239000004065 semiconductor Substances 0.000 title claims abstract description 33
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- 229910052751 metal Inorganic materials 0.000 claims abstract description 264
- 239000002184 metal Substances 0.000 claims abstract description 264
- 230000003647 oxidation Effects 0.000 claims abstract description 37
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 37
- 239000000463 material Substances 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims description 485
- 230000008569 process Effects 0.000 claims description 475
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 claims description 154
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 149
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 57
- 229910000510 noble metal Inorganic materials 0.000 claims description 10
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 10
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- 229910000449 hafnium oxide Inorganic materials 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 claims description 6
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 claims description 5
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052451 lead zirconate titanate Inorganic materials 0.000 claims description 4
- 229910000484 niobium oxide Inorganic materials 0.000 claims description 4
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims description 4
- 239000011669 selenium Substances 0.000 claims description 4
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 3
- RVSGESPTHDDNTH-UHFFFAOYSA-N alumane;tantalum Chemical compound [AlH3].[Ta] RVSGESPTHDDNTH-UHFFFAOYSA-N 0.000 claims description 3
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052454 barium strontium titanate Inorganic materials 0.000 claims description 3
- 229910052790 beryllium Inorganic materials 0.000 claims description 3
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 claims description 3
- HFGPZNIAWCZYJU-UHFFFAOYSA-N lead zirconate titanate Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ti+4].[Zr+4].[Pb+2] HFGPZNIAWCZYJU-UHFFFAOYSA-N 0.000 claims description 3
- 229910052702 rhenium Inorganic materials 0.000 claims description 3
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 3
- 229910052711 selenium Inorganic materials 0.000 claims description 3
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 claims description 3
- 229910001936 tantalum oxide Inorganic materials 0.000 claims description 3
- 229910052714 tellurium Inorganic materials 0.000 claims description 3
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- 201000002266 mite infestation Diseases 0.000 abstract 1
- 239000010408 film Substances 0.000 description 549
- 239000007789 gas Substances 0.000 description 263
- 235000012431 wafers Nutrition 0.000 description 149
- 239000012495 reaction gas Substances 0.000 description 46
- 239000003990 capacitor Substances 0.000 description 39
- 239000012159 carrier gas Substances 0.000 description 37
- 238000010926 purge Methods 0.000 description 35
- 239000004408 titanium dioxide Substances 0.000 description 27
- 230000007246 mechanism Effects 0.000 description 17
- 239000007788 liquid Substances 0.000 description 16
- 239000010936 titanium Substances 0.000 description 15
- 102100033121 Transcription factor 21 Human genes 0.000 description 14
- 101710119687 Transcription factor 21 Proteins 0.000 description 14
- 239000010410 layer Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 12
- 230000008016 vaporization Effects 0.000 description 12
- 238000005229 chemical vapour deposition Methods 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 9
- 238000011144 upstream manufacturing Methods 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 229910003855 HfAlO Inorganic materials 0.000 description 8
- 238000000137 annealing Methods 0.000 description 8
- 230000005587 bubbling Effects 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 238000000231 atomic layer deposition Methods 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 230000003247 decreasing effect Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 230000003028 elevating effect Effects 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- WKFBZNUBXWCCHG-UHFFFAOYSA-N phosphorus trifluoride Chemical compound FP(F)F WKFBZNUBXWCCHG-UHFFFAOYSA-N 0.000 description 7
- 238000001816 cooling Methods 0.000 description 6
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 6
- 238000009792 diffusion process Methods 0.000 description 5
- 238000009834 vaporization Methods 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 3
- 239000003779 heat-resistant material Substances 0.000 description 3
- 238000001465 metallisation Methods 0.000 description 3
- 150000004767 nitrides Chemical class 0.000 description 3
- 239000002356 single layer Substances 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(iv) oxide Chemical compound O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000011810 insulating material Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- MNWRORMXBIWXCI-UHFFFAOYSA-N tetrakis(dimethylamido)titanium Chemical compound CN(C)[Ti](N(C)C)(N(C)C)N(C)C MNWRORMXBIWXCI-UHFFFAOYSA-N 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical compound Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 description 1
- PIGFYZPCRLYGLF-UHFFFAOYSA-N Aluminum nitride Chemical compound [Al]#N PIGFYZPCRLYGLF-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910015801 BaSrTiO Inorganic materials 0.000 description 1
- 229910002367 SrTiO Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910007875 ZrAlO Inorganic materials 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910021332 silicide Inorganic materials 0.000 description 1
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000006200 vaporizer Substances 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having 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
- H01L21/28008—Making conductor-insulator-semiconductor electrodes
- H01L21/28017—Making conductor-insulator-semiconductor electrodes the insulator being formed after the semiconductor body, the semiconductor being silicon
- H01L21/28026—Making conductor-insulator-semiconductor electrodes the insulator being formed after the semiconductor body, the semiconductor being silicon characterised by the conductor
- H01L21/28088—Making conductor-insulator-semiconductor electrodes the insulator being formed after the semiconductor body, the semiconductor being silicon characterised by the conductor the final conductor layer next to the insulator being a composite, e.g. TiN
-
- 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
- C23C16/22—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 inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/34—Nitrides
-
- 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]
- C23C16/45527—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations
- C23C16/45529—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations specially adapted for making a layer stack of alternating different compositions or gradient compositions
-
- 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
- H01L21/28008—Making conductor-insulator-semiconductor electrodes
- H01L21/28017—Making conductor-insulator-semiconductor electrodes the insulator being formed after the semiconductor body, the semiconductor being silicon
- H01L21/28158—Making the insulator
- H01L21/28167—Making the insulator on single crystalline silicon, e.g. using a liquid, i.e. chemical oxidation
- H01L21/28194—Making the insulator on single crystalline silicon, e.g. using a liquid, i.e. chemical oxidation by deposition, e.g. evaporation, ALD, CVD, sputtering, laser deposition
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L28/00—Passive two-terminal components without a potential-jump or surface barrier for integrated circuits; Details thereof; Multistep manufacturing processes therefor
- H01L28/40—Capacitors
- H01L28/60—Electrodes
- H01L28/75—Electrodes comprising two or more layers, e.g. comprising a barrier layer and a metal layer
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices adapted for rectifying, amplifying, oscillating or switching, or capacitors or resistors with at least one potential-jump barrier or surface barrier, e.g. PN junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/40—Electrodes ; Multistep manufacturing processes therefor
- H01L29/43—Electrodes ; Multistep manufacturing processes therefor characterised by the materials of which they are formed
- H01L29/49—Metal-insulator-semiconductor electrodes, e.g. gates of MOSFET
- H01L29/4966—Metal-insulator-semiconductor electrodes, e.g. gates of MOSFET the conductor material next to the insulator being a composite material, e.g. organic material, TiN, MoSi2
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices adapted for rectifying, amplifying, oscillating or switching, or capacitors or resistors with at least one potential-jump barrier or surface barrier, e.g. PN junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/40—Electrodes ; Multistep manufacturing processes therefor
- H01L29/43—Electrodes ; Multistep manufacturing processes therefor characterised by the materials of which they are formed
- H01L29/49—Metal-insulator-semiconductor electrodes, e.g. gates of MOSFET
- H01L29/51—Insulating materials associated therewith
- H01L29/517—Insulating materials associated therewith the insulating material comprising a metallic compound, e.g. metal oxide, metal silicate
-
- 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
- H01L21/7687—Thin films associated with contacts of capacitors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/52—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames
- H01L23/522—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames including external interconnections consisting of a multilayer structure of conductive and insulating layers inseparably formed on the semiconductor body
- H01L23/5222—Capacitive arrangements or effects of, or between wiring layers
- H01L23/5223—Capacitor integral with wiring layers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/0001—Technical content checked by a classifier
- H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Computer Hardware Design (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Composite Materials (AREA)
- Ceramic Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Electrodes Of Semiconductors (AREA)
- Chemical Vapour Deposition (AREA)
- Semiconductor Memories (AREA)
- Semiconductor Integrated Circuits (AREA)
- Insulated Gate Type Field-Effect Transistor (AREA)
Abstract
Provided is a semiconductor device including a metal film which can be formed with lower costs but still mange to have a necessary work function and oxidation resistance. The semiconductor device includes an insulating film disposed on a substrate; and a metal film disposed adjacent to the insulating film. The metal film includes a stacked structure of a first metal film and a second metal film. The oxidation resistance of the first metal film is greater than that of the second metal film. The second metal film has a work function greater than 4.8 eV and is different from the first metal film in material. The first metal film is disposed between the second metal film and the insulating film.
Description
- This U.S. non-provisional patent application claims priority under 35 U.S.C. §119 of Japanese Patent Application No. 2010-002256, filed on Jan. 7, 2010, in the Japanese Patent Office, the entire contents of which are hereby incorporated by reference.
- 1. Field of the Invention
- The present invention relates to a semiconductor device, a method of manufacturing a semiconductor device, and a substrate processing apparatus.
- 2. Description of the Related Art
- To highly integrate metal-oxide-semiconductor field effect transistors (MOSFETs) and increase the performance of the MOSFETs, the use of a high-k/metal gate structure is considered, which is constituted by a gate insulating film made of a high permittivity insulating material (high-k material) and a gate electrode made of a metal. In the case of a p-channel metal-oxide semiconductor (PMOS) transistor, it is preferable that a gate electrode is made of a metal having a high work function of about 4.8 eV to 5.1 eV, and for example, it is considered that a gate electrode is made of a noble metal such as platinum (Pt).
- Furthermore, in the case of a dynamic random access memory (DRAM), it is considered that a capacitor insulating film is made of a high permittivity insulating material such as a hafnium dioxide (HfO2), a zirconium dioxide (ZrO2), a titanium dioxide (TiO2), a tantalum pentoxide (Ta2O5), and a niobium pentoxide (Nb2O5). In addition, a leak current of a capacitor part can be effectively reduced by forming a capacitor electrode using a metal having a high work function. Thus, when a capacitor insulating film is made of HfO2 or ZrO2 having a wide band gap, a capacitor electrode is made of a material such as a titanium nitride (TiN) having a work function of about 4.6 eV. In addition, when a capacitor insulating film is made of TiO2 or Nb2O5 having a narrow band gap, a capacitor electrode is made of a noble metal such as Pt having a high work function of about 5.1 eV.
- However, if a metal film (for example, a gate electrode, a capacitor electrode, etc.) is made of an expensive noble metal such as Pt, the manufacturing costs of a semiconductor device may be increased. In addition, it is difficult to form a thin film by using a noble metal such as Pt. It can be considered that another metal having a high work function such as nickel (Ni) or cobalt (Co) is used instead of a noble metal such as Pt. However, such a metal is easily oxidized, and if a metal film (a gate electrode or a capacitor electrode) is oxidized, the equivalent oxide thickness (EOT) of the metal film may be increased.
- An object of the present invention is to provide a semiconductor device including a metal film which can be formed with lower costs but have a necessary work function and oxidation resistance. Another object of the present invention is to provide a method of manufacturing a semiconductor device and a substrate processing apparatus, which are designed to form a metal film having a necessary work function and oxidation resistance with lower costs.
- According to an aspect of the present invention, there is provided a semiconductor device including: an insulating film disposed on a substrate; and a metal film disposed adjacent to the insulating film, wherein the metal film includes a stacked structure of a first metal film and a second metal film, an oxidation resistance of the first metal film is greater than that of the second metal film, the second metal film has a work function greater than 4.8 eV and is different from the first metal film in material, and the first metal film is disposed between the second metal film and the insulating film.
- According to another aspect of the present invention, there is provided a method of manufacturing a semiconductor device, the method including: forming an insulating film on a substrate; and forming a metal film including a stacked structure of a first metal film and a second metal film adjacent to the insulating film, the first metal film being formed between the second metal film and the insulating film, wherein an oxidation resistance of the first metal film is greater than that of the second metal film, and the second metal film has a work function greater than 4.8 eV and is different from the first metal film in material.
- According to another aspect of the present invention, there is provided a substrate processing apparatus including: a process chamber configured to process a substrate; a first process gas supply system configured to supply a first process gas into the process chamber to form a first metal film; a second process gas supply system configured to supply a second process gas into the process chamber to form a second metal film; and a controller configured to control the first process gas supply system and the second process gas supply system, wherein an oxidation resistance of the first metal film is greater than that of the second metal film, the second metal film has a work function greater than 4.8 eV and is different from the first metal film in material, and the controller controls the first process gas supply system and the second process gas supply system to form a metal film having a stacked structure of the first metal film and the second metal film adjacent to an insulating film disposed on the substrate by supplying the first process gas and the second process gas into the process chamber where the substrate is accommodated such that the first metal film is formed between the second metal film and the insulating film.
-
FIG. 1 is a flowchart for explaining substrate processing processes according to an embodiment of the present invention. -
FIG. 2 is a view illustrating a gas supply system of a substrate processing apparatus relevant to the embodiment of the present invention. -
FIG. 3 is a sectional view illustrating the substrate processing apparatus when a wafer is processed according to the embodiment of the present invention. -
FIG. 4 is a sectional view illustrating the substrate processing apparatus when a wafer is carried according to the embodiment of the present invention. -
FIG. 5A is a sectional view illustrating a gate electrode formed by performing a TiN film-forming process and a Ni film-forming process once, andFIG. 5B is sectional view illustrating a gate electrode formed by performing the TiN film-forming process and the Ni film-forming process a plurality of times. -
FIG. 6A is a sectional view illustrating a capacitor electrode formed by performing a TiN film-forming process and a Ni film-forming process once, andFIG. 6B is sectional view illustrating a capacitor electrode formed by performing the TiN film-forming process and the Ni film-forming process a plurality of times. -
FIG. 7 is a schematic view illustrating the energy level of a conventional capacitor electrode constituted by a single layer of TiN film. -
FIG. 8 is a schematic view illustrating the energy levels of a metal film formed by performing a TiN film-forming process and a Ni film-forming process once. -
FIG. 9 is a schematic view illustrating the energy levels of a metal film formed by setting a TiN film-forming process and a Ni film-forming process as one cycle and performing the cycle a plurality of times. -
FIG. 10 is a table illustrating a group of metals having work functions higher than 4.8 eV which can be used for forming a second metal film. -
FIG. 11 is a flowchart for explaining processes of forming an example 1 (sample B) and a comparative example (sample C) illustrated inFIG. 12 . -
FIG. 12 is a schematic view for explaining the stacked structure of the example 1 (sample B) of the present invention together with the stacked structure of a conventional example (sample A) and the stacked structure of the comparative example (sample C). -
FIG. 13 is a graph illustrating the equivalent oxide thicknesses (EOTs) of the samples A, B, and C illustrated inFIG. 12 . -
FIG. 14 is a graph illustrating relationships between leak current densities and EOTs of the respective samples A, B, and C illustrated inFIG. 12 . -
FIG. 15 is a graph illustrating relationships between leak current densities and applied voltages of the respective samples A, B, and C illustrated inFIG. 12 . -
FIG. 16A is a schematic view illustrating the stacked structure of an example 2 (sample D) of the present invention, andFIG. 16B is a graph illustrating a relationship between work function and TiN film thickness of the sample D together with those of the sample B and sample C. -
FIG. 17A andFIG. 17B are schematic views illustrating a vertical process furnace of a vertical apparatus according to another embodiment of the present invention, in whichFIG. 17A is a vertical sectional view illustrating the vertical process furnace andFIG. 17B is a sectional view of the vertical process furnace taken along line A-A ofFIG. 17A . -
FIG. 18 is a schematic view illustrating a cluster apparatus according to another embodiment of the present invention. - First, the structure of a substrate processing apparatus relevant to the current embodiment will be described with reference to
FIG. 3 andFIG. 4 .FIG. 3 is a sectional view illustrating the substrate processing apparatus when a wafer is processed according to an embodiment of the present invention, andFIG. 4 is a sectional view illustrating the substrate processing apparatus when the wafer is carried according to the embodiment of the present invention. - (Process Chamber)
- As shown in
FIG. 3 andFIG. 4 , the substrate processing apparatus relevant to the current embodiments includes aprocess vessel 202. For example, theprocess vessel 202 is a flat airtight vessel having a circular cross sectional shape. In addition, theprocess vessel 202 is made of a metal material such as aluminum or stainless steel (e.g., SUS described in the Japanese industrial standard). In theprocess vessel 202, aprocess chamber 201 is formed to process a substrate such as a wafer 200 (e.g., a silicon wafer). - (Support Stage)
- In the
process chamber 201, asupport stage 203 is installed to support awafer 200. On the top surface of thesupport stage 203 that makes direct contact with thewafer 200, asusceptor 217 made of a material such as quartz (SiO2), carbon, a ceramic material, silicon carbide (SiC), aluminum oxide (Al2O3), or aluminum nitride (AlN) is installed as a support plate. - In the
support stage 203, aheater 206 is built as a heating unit (heating source) configured to heat thewafer 200. The lower end part of thesupport stage 203 penetrates the bottom side of theprocess vessel 202. - (Elevating Mechanism)
- At the outside of the
process chamber 201, an elevatingmechanism 207 b is installed to raise and lower thesupport stage 203. By operating the elevatingmechanism 207 b to raise and lower thesupport stage 203, thewafer 200 supported on thesusceptor 217 can be raised and lowered. When thewafer 200 is carried, thesupport stage 203 is lowered to a position (wafer carrying position) shown inFIG. 4 , and when thewafer 200 is processed, thesupport stage 203 is raised to a position (wafer processing position) shown inFIG. 3 . The lower end part of thesupport stage 203 is surrounded by abellows 203 a so that the inside of theprocess chamber 201 can be hermetically maintained. - (Lift Pins)
- In addition, on the bottom surface (floor surface) of the
process chamber 201, for example, threelift pins 208 b are installed in a manner such that the lift pins 208 b are vertically erected. Furthermore, in the support stage 203 (including the susceptor 217), penetration holes 208 a are respectively formed at positions corresponding to the lift pins 208 b so that the lift pins 208 b can be inserted through the penetration holes 208 a. Therefore, when thesupport stage 203 is lowered to the wafer carrying position, as shown inFIG. 4 , upper parts of the lift pins 208 b protrude from the top surface of thesusceptor 217 so that the lift pins 208 b can support thewafer 200 from the bottom side of thewafer 200. - In addition, when the
support stage 203 is raised to the wafer processing position, as shown inFIG. 3 , the lift pins 208 b are retracted from the top surface of thesusceptor 217 so that thesusceptor 217 can support thewafer 200 from the bottom side of thewafer 2. Since the lift pins 208 b make direct contact with thewafer 200, it is preferable that the lift pins 208 b are made of a material such as quartz or alumina. - (Wafer Carrying Entrance)
- At a side of the inner wall of the process chamber 201 (process vessel 202), a
wafer carrying entrance 250 is installed so that awafer 200 can be carried into and out of theprocess chamber 201 throughwafer carrying entrance 250. At thewafer carrying entrance 250, agate valve 251 is installed so that the inside of theprocess chamber 201 can communicate with the inside of a carrying chamber (preliminary chamber) 271 by opening thegate valve 251. The carryingchamber 271 is formed in a carrying vessel (airtight vessel) 272. In the carryingchamber 271, a carryingrobot 273 is installed to carry awafer 200. The carryingrobot 273 includes a carryingarm 273 a to support awafer 200 when thewafer 200 is carried. In a state where thesupport stage 203 is lowered to the wafer carrying position, if thegate valve 251 is opened, awafer 200 can be carried between the inside of theprocess chamber 201 and the inside of the carryingchamber 271 by using the carryingrobot 273. Awafer 200 carried into theprocess chamber 201 is temporarily placed on the lift pins 208 b as described above. In addition, at a side of the carryingchamber 271 opposite to thewafer carrying entrance 250, a loadlock chamber (not shown) is installed, and awafer 200 can be carried between the inside of the loadlock chamber and the inside of the carryingchamber 271 by using the carryingrobot 273. The loadlock chamber is used as a preliminary chamber to temporarily accommodate a non-processed or processedwafer 200. - (Exhaust System)
- At a side of the inner wall of the process chamber 201 (process vessel 202) opposite to the
wafer carrying entrance 250, anexhaust outlet 260 is installed for exhausting the inside atmosphere of theprocess chamber 201. Anexhaust pipe 261 is connected to theexhaust outlet 260 through anexhaust chamber 260 a, and at theexhaust pipe 261, apressure regulator 262 such as an auto pressure controller (APC) configured to control the inside pressure of theprocess chamber 201, asource collection trap 263, and avacuum pump 264 are sequentially connected in series. An exhaust system (exhaust line) is constituted mainly by theexhaust outlet 260, theexhaust chamber 260 a, theexhaust pipe 261, thepressure regulator 262, thesource collection trap 263, and thevacuum pump 264. - (Gas Inlet)
- At the top surface (the ceiling wall) of a shower head 240 (described later) installed at an upper part of the
process chamber 201, agas inlet 210 is installed to introduce various gases into theprocess chamber 201. A gas supply system connected to thegas inlet 210 will be described later. - (Shower Head)
- Between the
gas inlet 210 and theprocess chamber 201, theshower head 240 is installed as a gas distributing mechanism. Theshower head 240 includes a distributingplate 240 a configured to distribute a gas introduced through thegas inlet 210, and ashower plate 240 b configured to distribute the gas passing through the distributingplate 240 a more uniformly and supply the gas to the surface of thewafer 200 placed on thesupport stage 203. A plurality of ventilation holes are formed in the distributingplate 240 a and theshower plate 240 b. The distributingplate 240 a is disposed to face the top surface of theshower head 240 and theshower plate 240 b, and theshower plate 240 b is disposed to face thewafer 200 placed on thesupport stage 203. Between the top surface of theshower head 240 and the distributingplate 240 a and between the distributingplate 240 a and theshower plate 240 b, spaces are provided which function as a first buffer space (distributing chamber) 240 c through which gas supplied through thegas inlet 210 is distributed and asecond buffer space 240 d through which gas passing through the distributingplate 240 a is diffused. - (Exhaust Duct)
- In the side surface of the inner wall of the process chamber 201 (process vessel 202), a
stopper 201 a is installed. Thestopper 201 a is configured to hold aconductance plate 204 at a position adjacent to the wafer processing position. Theconductance plate 204 is configured as a doughnut-shaped (ring-shaped) circular disk having an opening to accommodate thewafer 200 in its inner circumferential part. A plurality ofdischarge outlets 204 a are formed in the outer circumferential part of theconductance plate 204 in a manner such that thedischarge outlets 204 a are arranged at predetermined intervals in the circumferential direction of theconductance plate 204. Thedischarge outlets 204 a are discontinuously formed so that the outer circumferential part of theconductance plate 204 can support the inner circumferential part of theconductance plate 204. - A
lower plate 205 latches onto the outer circumferential part of thesupport stage 203. Thelower plate 205 includes a ring-shapedconcave part 205 b and aflange part 205 a formed in one piece with the inner upper side of theconcave part 205 b. Theconcave part 205 b is installed to close a gap between the outer circumferential part of thesupport stage 203 and the side surface of the inner wall of theprocess chamber 201. At a part of the lower side of theconcave part 205 b adjacent to theexhaust outlet 260, aplate exhaust outlet 205 c is formed to discharge (distribute) gas from the inside of theconcave part 205 b toward theexhaust outlet 260. Theflange part 205 a functions as a latching part that latches onto the upper outer circumferential part of thesupport stage 203. Since theflange part 205 a latches onto the upper outer circumferential part of thesupport stage 203, thelower plate 205 can be lifted together with thesupport stage 203 when thesupport stage 203 is lifted. - When the
support stage 203 is raised to the wafer processing position, thelower plate 205 is also raised to the wafer processing position. As a result, the top surface of theconcave part 205 b of thelower plate 205 is blocked by theconductance plate 204 held at a position adjacent to the wafer processing position, and thus a gas flow passage region is formed in theconcave part 205 b as anexhaust duct 259. At this time, by the exhaust duct 259 (theconductance plate 204 and the lower plate 205) and thesupport stage 203, the inside of theprocess chamber 201 is divided into an upper process chamber higher than theexhaust duct 259 and a lower process chamber lower than theexhaust duct 259. Preferably, theconductance plate 204 and thelower plate 205 may be formed of a material that is durable at a high temperature, for example, high temperature resistant and high load resistant quartz, for the case where reaction products deposited on the inner wall of theexhaust duct 259 are etched away (for the case of self cleaning). - An explanation will now be given on a gas flow in the
process chamber 201 during a wafer processing process. First, gas supplied from thegas inlet 210 to the upper side of theshower head 240 flows from the first buffer space (distributing chamber) 240 c to thesecond buffer space 240 d through the plurality of holes of the distributingplate 240 a, and is then supplied to the inside of theprocess chamber 201 through the plurality of holes of theshower plate 240 b, so that the gas can be uniformly supplied to thewafer 200. Then, the gas supplied to thewafer 200 flows outward in the radial directions of thewafer 200. After the gas makes contact with thewafer 200, remaining gas is discharged to theexhaust duct 259 disposed at the outer circumference of the wafer 200: that is, the remaining gas flows outward on theconductance plate 204 in the radial directions of thewafer 200 and is discharged to the gas flow passage region (the inside of theconcave part 205 b) of theexhaust duct 259 through thedischarge outlets 204 a formed in theconductance plate 204. Thereafter, the gas flows in theexhaust duct 259 and is exhaust through theplate exhaust outlet 205 c and theexhaust outlet 260. Since gas is guided to flow in this manner, the gas may be prevented from flowing to the lower part of theprocess chamber 201. That is, the gas may be prevented from flowing to the rear side of thesupport stage 203 or the bottom side of theprocess chamber 201. - <Gas Supply System>
- Next, the configuration of the gas supply system connected to the
gas inlet 210 will be described with reference toFIG. 2 .FIG. 2 illustrates the configuration of the gas supply system (gas supply lines) of the substrate processing apparatus relevant to the embodiment of the present invention. - The gas supply system of the substrate processing apparatus of the current embodiment includes: a bubbler as a vaporizing unit configured to vaporize a liquid source which is liquid at room temperature; a source gas supply system configured to supply a source gas, which is obtained by vaporizing the liquid source using the bubbler, into the
process chamber 201; and a reaction gas supply system configured to supply a reaction gas different from the source gas into theprocess chamber 201. In addition, the substrate processing apparatus of the current embodiment includes a purge gas supply system configured to supply a purge gas into theprocess chamber 201, and a vent (bypass) system so as not to supply a source gas generated from the bubbler into theprocess chamber 201 but to exhaust the source gas through a passage bypassing theprocess chamber 201. Next, the structure of each part will be described. - <Bubbler>
- At the outside of the
process chamber 201, a first source container (first bubbler) 220 a is installed which contains a first source (source A) which is a liquid source, and a second source container (second bubbler) 220 b is installed which contains a second source (source B) which is a liquid source. Each of the first andsecond bubblers bubblers first bubbler 220 a and thesecond bubbler 220 b to heat the first andsecond bubblers second bubblers - A first carrier
gas supply pipe 237 a and a second carriergas supply pipe 237 b are connected to thefirst bubbler 220 a and thesecond bubbler 220 b, respectively. Carrier gas supply sources (not shown) are connected to the upstream end parts of the first carriergas supply pipe 237 a and the second carriergas supply pipe 237 b. In addition, the downstream end parts of the first carriergas supply pipe 237 a and the second carriergas supply pipe 237 b are placed in the liquid sources filled in thefirst bubbler 220 a and thesecond bubbler 220 b, respectively. A mass flow controller (MFC) 222 a which is a flow rate controller configured to control the supply flow rate of a carrier gas, and valves va1 and va2 configured to control supply of the carrier gas are installed at the first carriergas supply pipe 237 a. A mass flow controller (MFC) 222 b which is a flow rate controller configured to control the supply flow rate of a carrier gas, and valves vb1 and vb2 configured to control supply of the carrier gas are installed at the second carriergas supply pipe 237 b. Preferably, a gas that does not react with the liquid sources may be used as the carrier gas. For example, inert gas such as N2 gas and Ar gas may be used as the carrier gas. A first carrier gas supply system (first carrier gas supply line) is constituted mainly by the first carriergas supply pipe 237 a, theMFC 222 a, and the valves va1 and va2, and a second carrier gas supply system (second carrier gas supply line) is constituted mainly by the second carriergas supply pipe 237 b, theMFC 222 b, and the valves vb1 and vb2. - In the above-described structure, the valves va1, va2, vb1, and vb2 are opened, and a carrier gas the flow rates of which are controlled by the
MFC 222 a and theMFC 222 b is supplied from the first carriergas supply pipe 237 a and the second carriergas supply pipe 237 b into thefirst bubbler 220 a and thesecond bubbler 220 b. Then, the liquid sources filled in the first andsecond bubblers - The supply flow rates of the first source gas and the second source gas may be calculated from the supply flow rates of the carrier gas. That is, the supply flow rates of the first source gas and the second source gas may be controlled by adjusting the supply flow rates of the carrier gas.
- <Source Gas Supply System>
- A first source
gas supply pipe 213 a and a second sourcegas supply pipe 213 b are respectively connected to thefirst bubbler 220 a and thesecond bubbler 220 b to supply the first source gas and the second source gas generated in thefirst bubbler 220 a and thesecond bubbler 220 b into theprocess chamber 201. The upstream end parts of the first and second sourcegas supply pipes second bubblers gas supply pipes gas inlet 210. - In addition, valves va5 and va3 are sequentially installed from the upstream side of the first source
gas supply pipe 213 a. The valve va5 is configured to control supply of the first source gas from thefirst bubbler 220 a to the first sourcegas supply pipe 213 a, and the valve va5 is installed at a position adjacent to thefirst bubbler 220 a. The valve va3 is configured to control supply of the first source gas from the first sourcegas supply pipe 213 a to theprocess chamber 201, and the valve va3 is installed at a position adjacent to thegas inlet 210. In addition, valves vb5 and vb3 are sequentially installed from the upstream side of the second sourcegas supply pipe 213 b. The valve vb5 is configured to control supply of the second source gas from thesecond bubbler 220 b to the second sourcegas supply pipe 213 b, and the valve vb5 is installed at a position adjacent to thesecond bubbler 220 b. The valve vb3 is configured to control supply of the second source gas from the second sourcegas supply pipe 213 b to theprocess chamber 201, and the valve vb3 is installed at a position adjacent to thegas inlet 210. The valves va3 and vb3, and a valve ve3 (described later) are highly-durable, high-speed valves. Highly-durable, high-speed valves are integrated valves configured to rapidly switch supply of gas, interruption of gas supply, and exhaustion of gas. The valve ve3 controls introduction of a purge gas so as to rapidly purge a space of the first sourcegas supply pipe 213 a between the valve va3 and thegas inlet 210 and a space of the second sourcegas supply pipe 213 b between the valve vb3 and thegas inlet 210, and then to purge the inside of theprocess chamber 201. - In the above-described structure, the liquid sources are vaporized in the first and
second bubblers process chamber 201 from the first and second sourcegas supply pipes gas supply pipe 213 a and the valve va5 and va3, and a second source gas supply system (second source gas supply line) is constituted mainly by the second sourcegas supply pipe 213 b and the valves vb5 and vb3. - A first source supply system (first source supply line) is constituted mainly by the first carrier gas supply system, the
first bubbler 220 a, and the first source gas supply system; and a second source supply system (second source supply line) is constituted mainly by the second carrier gas supply system, thesecond bubbler 220 b, and the second source gas supply system. A first process gas supply system is constituted by the first source supply system and a reaction gas supply system (described later), and a second process gas supply system is constituted by the second source gas supply system. - <Reaction Gas Supply System>
- In addition, at the outside of the
process chamber 201, a reactiongas supply source 220 c is installed to supply a reaction gas. The upstream end part of a reactiongas supply pipe 213 c is connected to the reactiongas supply source 220 c. The downstream end part of the reactiongas supply pipe 213 c is connected to thegas inlet 210 through a valve vc3. AnMFC 222 c which is a flow rate controller configured to control the supply flow rate of a reaction gas, and valves vc1 and vc2 configured to control supply of the reaction gas are installed at the reactiongas supply pipe 213 c. For example, ammonia (NH3) gas may be used as the reaction gas. A reaction gas supply system (reaction gas supply line) is constituted mainly by the reactiongas supply source 220 c, the reactiongas supply pipe 213 c, theMFC 222 c, and the valves vc1, vc2, and vc3. - <Purge Gas Supply System>
- In addition, at the outside of the
process chamber 201, purgegas supply sources gas supply pipes 213 d and 213 e are connected to the purgegas supply sources gas supply pipe 213 d is joined to the reactiongas supply pipe 213 c and is connected to thegas inlet 210 through the valve vc3. The downstream end part of the purge gas supply pipe 213 e is joined to the first sourcegas supply pipe 213 a and the second sourcegas supply pipe 213 b and is connected to thegas inlet 210 through the valve ve3. At the purgegas supply pipes 213 d and 213 e,MFCs gas supply sources gas supply pipes 213 d and 213 e, theMFCs - <Vent (Bypass) System>
- In addition, the upstream end parts of a
first vent pipe 215 a and asecond vent pipe 215 b are respectively connected to the upstream sides of the valves va3 and vb3 of the first and second sourcegas supply pipes second vent pipes pressure regulator 262 and the upstream side of thesource collection trap 263 of theexhaust pipe 261. At the first andsecond vent pipes - In the above-described structure, by closing the valves va3 and vb3 and opening the valves va4 and vb4, gases flowing in the first and second source
gas supply pipes process chamber 201 through the first andsecond vent pipes process chamber 201, and then the gases can be exhausted to the outside of theprocess chamber 201 through theexhaust pipe 261. A first vent system is constituted mainly by thefirst vent pipe 215 a, the valve va4, and a second vent system is constituted mainly by thesecond vent pipe 215 b and the valve vb4. - The sub-heaters 206 a are also installed around the first and
second vent pipes gas supply pipe 237 a, the second carriergas supply pipe 237 b, the first sourcegas supply pipe 213 a, the second sourcegas supply pipe 213 b, theexhaust pipe 261, theprocess vessel 202, and theshower head 240. The sub-heater 206 a is configured to heat such members to, for example, 100° C. or lower, so as to prevent the first and second source gases from changing back to liquid in the members. - <Controller>
- The substrate processing apparatus relevant to the current embodiment includes a
controller 280 configured to control each part of the substrate processing apparatus. Thecontroller 280 controls operations of parts such as thegate valve 251, the elevatingmechanism 207 b, the carryingrobot 273, theheater 206, the sub-heater 206 a, the pressure regulator (APC) 262, thevacuum pump 264, the valves va1 to va5, vb1 to vb5, vc1 to vc3, vd1 and vd2, and ve1 to ve3, and theMFCs - Next, with reference to
FIG. 1 , as one of semiconductor device manufacturing processes, a substrate processing process for forming a thin film on a wafer by a chemical vapor deposition (CVD) method and an atomic layer deposition (ALD) method using the above-described substrate processing apparatus will be explained according to the embodiment of the present invention.FIG. 1 is a flowchart for explaining substrate processing processes according to the embodiment of the present invention. In the following description, operations of parts constituting the substrate processing apparatus are controlled by thecontroller 280. - In the following description, an explanation will be given on an exemplary case where a metal film having a stacked structure constituted by a TiN film being a first metal film and a Ni film being a second metal film is formed on a TiO2 film which is previously formed on a substrate such as a
wafer 200 as an insulating film (gate insulating film or capacitor insulating film). - The TiN film which is a first metal film is formed according to an ALD method by alternately supplying a first source gas (Ti source), which is generated by vaporizing a first source (TiCl4), and a reaction gas (NH3 gas) into the
process chamber 201 in which thewafer 200 is accommodated. The Ni film which is a second metal film is formed according to a CVD method by supplying a second source gas (Ni source) generated by vaporizing a second source (Ni(PF3)4) into theprocess chamber 201 in which thewafer 200 is accommodated. The first source gas and the reaction gas constitute a first process gas, and the second source gas constitutes a second process gas. - In this specification, the term “metal film” is used to denote a film formed of a conductive material containing metal atoms. Examples thereof include a conductive elemental metal film formed of an elemental metal, a conductive metal nitride film, a conductive metal oxide film, a conductive metal oxynitride film, a conductive metal composite film, a conductive metal alloy film, and a conductive metal silicide film. The TiN film is a conductive metal nitride film, and the Ni film is a conductive elemental metal film. The exemplary case will now be explained in detail.
- <Substrate carrying-in process S1, Substrate placing process S2>
- First, the elevating
mechanism 207 b is operated to lower thesupport stage 203 to the wafer carrying position as shown inFIG. 4 . Next, thegate valve 251 is opened so that theprocess chamber 201 can communicate with the carryingchamber 271. Next, awafer 200 to be processed is carried from the carryingchamber 271 to theprocess chamber 201 by using the carryingrobot 273 in a state where thewafer 200 is supported on the carryingarm 273 a (S1). A TiO2 film is previously formed as an insulating film (gate insulating film or capacitor insulating film) on thewafer 200 to be processed. Thewafer 200 loaded in theprocess chamber 201 is temporarily placed on the lift pins 208 b which protrude upward from the top surface of thesupport stage 203. Thereafter, the carryingarm 273 a of the carryingrobot 273 is moved from the inside of theprocess chamber 201 back to the carryingchamber 271, and thegate valve 251 is closed. - Next, the elevating
mechanism 207 b is operated to raise thesupport stage 203 to the wafer processing position as shown inFIG. 3 . As a result, the lift pins 208 b are retracted from the top surface of thesupport stage 203, and thewafer 200 is placed on thesusceptor 217 disposed at the top surface of the support stage 203 (S2). - <Pressure Adjusting Process S3, Temperature Adjusting Process S4)
- Subsequently, by using the pressure regulator (APC) 262, the inside pressure of the
process chamber 201 is adjusted to a predetermined process pressure (S3). In addition, power supplied to theheater 206 is controlled to increase the surface temperature of thewafer 200 to a predetermined process temperature (S4). The temperature adjusting process S4 may be performed in parallel with or prior to the pressure adjusting process S3. The predetermined process temperature and process pressure are set in a manner such that a TiN film can be formed in a TiN film-forming process S5 (described later) by an ALD method. That is, the process temperature and the process pressure are set in a manner such that a first source gas supplied in a Ti source supply process S5 a does not decompose by itself In the substrate carrying-in process 51, the substrate placing process S2, the pressure adjusting process S3, and the temperature adjusting process S4, thevacuum pump 264 is operated in a state where the valves va3 and vb3 are closed and the valves vd1, vd2, vc3, ve1, ve2, and ve3 are opened, so as to create a flow of N2 gas in theprocess chamber 201. By this, adhesion of particles to thewafer 200 can be suppressed. - Along with the processes S1 to S4, a first source (TiCl4) is vaporized to generate a first source gas (Ti source). That is TiCl4 gas is generated (preliminary vaporization). That is, the valves va1, va2, and va5 are opened, and a carrier gas the flow rate of which is controlled by the
MFC 222 a is supplied from the first carriergas supply pipe 237 a into thefirst bubbler 220 a so as to vaporize a first source filled in thefirst bubbler 220 a by bubbling to generate a first source gas (preliminary vaporization process). In this preliminary vaporization process, while operating thevacuum pump 264, the valve va4 is opened in a state where the valve va3 is closed, so that the first source gas is not supplied into to theprocess chamber 201 but is exhausted through a route bypassing theprocess chamber 201. A predetermined time is necessary for thefirst bubbler 220 a to stably generate the first source gas. For this reason, in the current embodiment, the first source gas is preliminary generated, and the flow passage of the first source gas is changed by selectively opening and closing the valves va3 and va4. That is, by selectively opening and closing the valves va3 and va4, stable supply of the first source gas into theprocess chamber 201 can be quickly started and stopped. This operation is preferable. - <TiN Film-Forming Process S5>
- (Ti Source Supply Process S5 a)
- Next, while operating the
vacuum pump 264, the valve va4 is closed and the valve va3 is opened to start supply of the first source gas (Ti source) into theprocess chamber 201. - The first source gas is distributed by the
shower head 240 so that the first source gas can be uniformly supplied to thewafer 200 disposed in theprocess chamber 201. Surplus first source gas flows in theexhaust duct 259 and is exhausted to theexhaust outlet 260 and theexhaust pipe 261. At this time, the process temperature and process pressure are set in a manner such that the first source gas does not decompose by itself. Therefore, molecules of the first source gas are adsorbed on the TiO2 film which is previously formed on thewafer 200 as an insulating film (gate insulating film or capacitor insulating film). - When the first source gas is supplied into the
process chamber 201, so as to prevent permeation of the first source gas into the reactiongas supply pipe 213 c and facilitate diffusion of the first source gas in theprocess chamber 201, it is preferable that the valves ve1, vc2, and vc3 are kept in an opened state to continuously supply N2 gas into theprocess chamber 201. - After a predetermined time from the start of supply of the first source gas by opening the valve va3, the valve va3 is closed, and the valves va4 is opened to stop supply of the first source gas into the
process chamber 201. - (Purge Process S5 b)
- After stopping supply of the first source gas by closing the valve va3, the valves vd1, vd2, vc3, ve1, ve2, and ve3 are opened to supply N2 gas into the
process chamber 201. The N2 gas is dispersed by theshower head 240 and uniformly supplied to thewafer 200 disposed in theprocess chamber 201, and then the N2 gas flows in theexhaust duct 259 and is exhausted to theexhaust outlet 260 and theexhaust pipe 261. In this way, the first source gas remaining in theprocess chamber 201 is removed, and the inside of theprocess chamber 201 is purged with N2 gas. - (Reaction Gas Supply Process S5 c)
- After the inside of the
process chamber 201 is purged, the valves vc1, vc2, and vc3 are opened to start supply of a reaction gas (NH3 gas) into theprocess chamber 201. The reaction gas is dispersed by theshower head 240 and uniformly supplied to thewafer 200 disposed in theprocess chamber 201 so that the reaction gas reacts with the molecules of the first source gas adsorbed on the TiO2 film previously formed on thewafer 200. Thus, a TiN film constituted by about less than one atomic layer (less than 1 Å) is formed on the TiO2 film. Surplus reaction gas or reaction byproducts are allowed to flow in theexhaust duct 259 and are exhausted to theexhaust outlet 260 and theexhaust pipe 261. After a predetermined time from the start of supply of the reaction gas by opening the valve vc1, vc2, and vc3, the supply of the reducing gas into theprocess chamber 201 is interrupted by closing the valves vc1 and vc2. - When the reaction gas is supplied into the
process chamber 201, so as to prevent permeation of the reaction gas into the first sourcegas supply pipe 213 a and the second sourcegas supply pipe 213 b and facilitate diffusion of the reaction gas in theprocess chamber 201, it is preferable that the valves ve1, ve2, and ve3 are kept opened to continue supply of N2 gas into theprocess chamber 201. - (Purge Process S5 d)
- After stopping supply of the reaction gas by closing the valve vc1 and vc2, the valves vd1, vd2, vc3, ve1, ve2, and ve3 are opened to supply N2 gas into the
process chamber 201. The N2 gas is dispersed by theshower head 240 and uniformly supplied to thewafer 200 disposed in theprocess chamber 201, and then the N2 gas flows in theexhaust duct 259 and is exhausted to theexhaust outlet 260 and theexhaust pipe 261. - In this way, reaction gas and reaction byproducts remaining in the
process chamber 201 are removed, and the inside of theprocess chamber 201 is purged with the N2 gas. - (Predetermined-Time Executing Process S5 e)
- The Ti source supply process S5 a, the purge process S5 b, the reaction gas supply process S5 c, and the purge process S5 d are set as one cycle, and the cycle (ALD cycle) is performed predetermined times (n1 cycles) so that a titanium nitride (TiN) film having a predetermined thickness can be formed as a first metal film on the TiO2 film previously formed on the
wafer 200. The TiN film which is a first metal film has an oxidation resistance greater than that of a Ni film that will be formed as a second metal film (described later). - <Pressure Adjusting Process S6, Temperature Adjusting Process S7)
- Subsequently, by using the pressure regulator (APC) 262, the inside pressure of the
process chamber 201 is adjusted to a predetermined process pressure (S6). In addition, power supplied to theheater 206 is controlled to increase the surface temperature of thewafer 200 to a predetermined process temperature (S7). The temperature adjusting process S7 may be performed in parallel with or prior to the pressure adjusting process S6. The predetermined process temperature and process pressure are set in a manner such that a Ni film can be formed in a Ni film-forming process S8 (described later) by a CVD method. That is, the process temperature and the process pressure are set in a manner such that a second source gas supplied in a Ni source supply process S8 a can decompose by itself. - Along with the pressure adjusting process S6 and the temperature adjusting process S7, a second source (Ni(PF3)4) is vaporized to previously generate a second source gas (Ni source), that is, Ni(PF3)4 gas for the next Ni film-forming process S8 (preliminary vaporization). That is, the valves vb1, vb2, and vb5 are opened, and a carrier gas, the flow rate of which is controlled by the
MFC 222 b, is supplied from the second carriergas supply pipe 237 b into thesecond bubbler 220 b so as to vaporize a second source filled in thesecond bubbler 220 b by bubbling to generate a second source gas (preliminary vaporization process). In this preliminary vaporizing process, while operating thevacuum pump 264, the valve vb4 is opened in a state where the vb3 is closed so as not to supply the second source gas into theprocess chamber 201 but exhaust the second source gas through a route bypassing theprocess chamber 201. A predetermined time is necessary for thesecond bubbler 220 b to stably generate the second source gas. For this reason, in the current embodiment, the second source gas is preliminary generated, and the flow passage of the second source gas is changed by selectively opening and closing the valves vb3 and vb4. That is, by selectively opening and closing the valves vb3 and vb4, stable supply of the second source gas into theprocess chamber 201 can be quickly started and stopped. This operation is preferable. - <Ni Film-Forming Process S8>
- (Ni Source Supply Process S8 a)
- Next, while operating the
vacuum pump 264, the valve va4 is closed and the valve va3 is opened to supply the second source gas (Ni source) into theprocess chamber 201. The second source gas is distributed by theshower head 240 so that the second source gas can be uniformly supplied to thewafer 200 disposed in theprocess chamber 201. Surplus second source gas flows in theexhaust duct 259 and is exhausted to theexhaust outlet 260 and theexhaust pipe 261. At this time, the process temperature and process pressure are set in a manner such that the second source gas can decompose. Therefore, the second source gas supplied to thewafer 200 thermally decomposes and participates in a CVD reaction, and accordingly a Ni film is formed on thewafer 200. - When the second source gas is supplied into the
process chamber 201, so as to prevent permeation of the second source gas into the reactiongas supply pipe 213 c and facilitate diffusion of the second source gas in theprocess chamber 201, it is preferable that the valves vd1, vd2, and vd3 are kept in an opened state to continuously supply N2 gas into theprocess chamber 201. - After a predetermined time from the start of supply of the second source gas by opening the valve vb3, the valve vb3 is closed and the valves vb4 is opened to stop supply of the second source gas into the
process chamber 201. - (Purge Process S8 b)
- After stopping supply of the second source gas by closing the valve vb3, the valves vd1, vd2, vc3, ve1, ve2, and ve3 are opened to supply N2 gas into the
process chamber 201. The N2 gas is dispersed by theshower head 240 and supplied into theprocess chamber 201, and then the N2 gas flows in theexhaust duct 259 and is exhausted to theexhaust outlet 260 and theexhaust pipe 261. In this way, the second source gas remaining in theprocess chamber 201 is removed, and the inside of theprocess chamber 201 is purged with N2 gas. - (Predetermined-Time Executing Process S8 c)
- The Ni source supply process S8 a and the purge process S8 b are set as one cycle, and the cycle is performed predetermined times (n2 cycles) so that a nickel film (Ni film) having a predetermined thickness can be formed as a second metal film on the TiN film which is formed as a first metal film over the
wafer 200. The Ni film which is a second metal film is made of a material having a work function greater than 4.8 eV and different from a material used to form the first metal film. - <Predetermined-Time Executing Process S9>
- The pressure adjusting process S3 to the TiN film-forming process S5 and the pressure adjusting process S6 to the Ni film-forming process S8 are set as one cycle, and the cycle is performed predetermined times (n3 cycles) so that a metal film having a stacked structure constituted by the TiN film being the first metal film and the Ni film being the second metal film can be formed on the TiO2 film previously formed on the
wafer 200. As described above, the TiN film which is the first metal film has an oxidation resistance greater than the oxidation resistance of the Ni film which is the second metal film. In addition, the Ni film which is the second metal film is made of a material having a work function greater than 4.8 eV and being different from the first metal film. The TiN film which is the first metal film is formed between the Ni film (second metal film) and the TiO2 film. - <Pressure Adjusting Process S10, Temperature Adjusting Process S11)
- Next, like in the pressure adjusting process S3 and the temperature adjusting process S4, the inside pressure of the
process chamber 201 is adjusted to a predetermined process pressure (S10), and the surface temperature of thewafer 200 is adjusted to a predetermined process temperature (S11). - <TiN Cap Forming Process S12>
- (Ti Source Supply Process S12 a)
- Next, like in the Ti source supply process S5 a, the first source gas (Ti source) is supplied into the
process chamber 201 for a predetermined time, and then the supply of the first source gas into theprocess chamber 201 is stopped. - (Purge Process S12 b)
- After stopping the supply of first source gas, the inside of the
process chamber 201 is purged with N2 gas like in the purge process S5 b. - (Reaction Gas Supply Process S12 c)
- After the inside of the
process chamber 201 is purged, like in the reaction gas supply process S5 c, the reaction gas (NH3 gas) is supplied into theprocess chamber 201 for a predetermined time, and then the supply of the reaction gas into theprocess chamber 201 is stopped. - (Purge Process S12 d)
- After stopping the supply of the reaction gas, the inside of the
process chamber 201 is purged with N2 gas like in the purge process S5 d. - (Predetermined-Time Executing Process S12 e)
- The Ti source supply process S12 a, the purge process S12 b, the reaction gas supply process S12 c, and the purge process S12 d are set as one cycle, and the cycle is performed predetermined times (n4 cycles) so that a TiN film (TiN cap film) having a predetermined thickness can be formed as a first metal film on the metal film (having a stacked structure constituted by TiN film and Ni film) formed through the predetermined-time executing process S9.
- By performing the processes S3 to S12, the metal film can be formed adjacent to the TiO2 film which is previously formed on the
wafer 200 as an insulating film (gate insulating film or capacitor insulating film). The metal film has a stacked structure constituted by the TiN film which is the first metal film and the Ni film which is the second metal film. The first metal film is made of a material (TiN) having an oxidation resistance greater than the oxidation resistance of the second metal film, and the second metal film is made of a material (Ni) having a work function greater than 4.8 eV and being different from the material used to make the first metal film. In addition, the TiN film is formed between the Ni film and the TiO2 film. Furthermore, the TiN film (TiN cap film) is formed on the outermost surface of the metal film. If the execution number (n3 cycles) of the predetermined-time executing process S9 is set to one (one cycle), a metal film can be formed as a gate electrode as shown inFIG. 5A or a top capacitor electrode as shown inFIG. 6A . If the execution number (n3 cycles) of the predetermined-time executing process S9 is set to two or more (two or more cycles), a metal film can be formed as a gate electrode as shown inFIG. 5B or a top capacitor electrode as shown inFIG. 6B . A bottom capacitor electrode as shown inFIG. 6B may also be formed through a process similar to the process of forming the top capacitor electrode. - <Remaining Gas Removing Process S13>
- After the TiN cap film having a predetermined thickness is formed on the metal film (having a stacked structure constituted by TiN film and Ni film) formed through the predetermined-time executing process S9, the inside of the
process chamber 201 is vacuum-evacuated, and the valves vd1, vd2, vc3, ve1, ve2, and ve3 are opened to supply N2 gas into theprocess chamber 201. The N2 gas is dispersed by theshower head 240 and supplied into theprocess chamber 201, and then the N2 is exhausted to theexhaust pipe 261. In this way, gas and reaction byproducts remaining in theprocess chamber 201 are removed, and the inside of theprocess chamber 201 is purged with the N2 gas. - <Substrate Carrying-Out Process S14>
- Thereafter, in the reverse order to that of the substrate carrying-in process S1 and the substrate placing process S2, the
wafer 200, over which the metal film (having a stacked structure constituted by TiN film and Ni film) and the TiN cap film are formed to predetermined thicknesses, is carried out from theprocess chamber 201 to the carryingchamber 271, thereby completing the substrate processing process of the current embodiment. - Furthermore, in the current embodiment, the TiN film-forming process S5 may be performed to a
wafer 200 under the following exemplary conditions. - Process temperature: 250° C. to 550° C., preferably, 350° C. to 550° C.,
- Process pressure: 50 Pa to 5,000 Pa,
- Supply flow rate of carrier gas (N2) for bubbling: 10 sccm to 1,000 sccm,
- Supply flow rate of first source gas (TiCl4): 0.1 sccm to 2 sccm,
- Supply flow rate of reaction gas (NH3): 10 sccm to 1,000 sccm,
- Supply flow rate of purge gas (N2): 100 sccm to 10,000 sccm, and
- Film thickness (TiN film): 0.2 nm to 4 nm.
- Furthermore, in the current embodiment, the Ni film-forming process S8 may be performed to a
wafer 200 under the following exemplary conditions. - Process temperature: 150° C. to 250° C., preferably, 150° C. to 200° C.,
- Process pressure: 50 Pa to 5,000 Pa,
- Supply flow rate of carrier gas (N2) for bubbling: 10 sccm to 1,000 sccm,
- Supply flow rate of second source gas (Ni(PF3)4): 0.1 sccm to 2 sccm,
- Supply flow rate of purge gas (N2): 100 sccm to 10,000 sccm, and
- Film thickness (Ni film): 0.5 nm to 10 nm, preferably, 4 nm to 5 nm.
- In addition, total film thickness in the predetermined-time executing process S9, that is, the thickness of a metal film having a stacked structure constituted by TiN film being first metal film and Ni film being second metal film may be, for example, 10 nm to 30 nm.
- Furthermore, in the current embodiment, the TiN cap film-forming process S12 may be performed to a
wafer 200 under the following exemplary conditions. - Process temperature: 250° C. to 550° C., preferably, 350° C. to 550° C.,
- Process pressure: 50 Pa to 5,000 Pa,
- Supply flow rate of carrier gas (N2) for bubbling: 10 sccm to 1,000 sccm,
- Supply flow rate of first source gas (TiCl4): 0.1 sccm to 2 sccm,
- Supply flow rate of reaction gas (NH3): 10 sccm to 1,000 sccm,
- Supply flow rate of purge gas (N2): 100 sccm to 10,000 sccm, and
- Film thickness (TiN film): 0.2 nm to 50 nm, preferably, 1 nm to 10 nm.
- If a TiN film is formed to have a thickness of less than 0.2 nm in the TiN film-forming process S5, the TiN film may not be constituted by one or more continuous layers between a Ni film and a TiO2 film. That is, the TiN film may be constituted by a discontinuous layer, and thus the Ni film and the TiO2 may make contact with each other. Therefore, an oxygen component included in the TiO2 film may permeate into the Ni film through a contact part, and thus the Ni film may be oxidized. In addition, if a TiN film is formed to have a thickness greater than 4 nm in the TiN film-forming process S5, the effective work function of an entire metal film may not be the work function of a Ni film (about 5.15 eV) but may be close to the work function of the TiN film (about 4.6 eV). Thereafter, it is preferable that a TiN film is formed to have a thickness of 0.2 nm to 4 nm in the TiN film-forming process S5.
- In addition, if the process temperature of the Ni film-forming process S8 is lower than 150° C., in the Ni film-forming process S8 a, the second source (Ni(PF3)4) may not decompose by itself, and thus, a CVD film-forming reaction may not occur. In addition, if the process temperature is higher than 250° C. in a state where the process pressure is kept in the above-mentioned range, the film-forming rate may increase excessively, and thus it may be difficult to control a film thickness. Therefore, in the Ni film-forming process S8, it is necessary to keep the process temperature in the range from 150° C. to 250° C. for inducing a CVD film-forming reaction and controlling a film thickness.
- In the current embodiment, it is preferable that the TiN film-forming process S5 and the Ni film-forming process S8 are performed at the same process temperature and/or the same process pressure. That is, in the current embodiment, it is preferable that the TiN film-forming process S5 and the Ni film-forming process S8 are performed at a constant process temperature and/or a constant process pressure. If the process temperature and the process pressure are set to predetermined values in the above-mentioned ranges, ALD film formation and CVD film formation can be performed under the same conditions. In this case, when the procedure goes from the TiN film-forming process S5 to the Ni film-forming process S8 or from the Ni film-forming process S8 to the TiN film-forming process S5, a process of changing the process temperature and a process of changing the process pressure may not be necessary, and thus the throughput may be improved.
- According to the current embodiment, one or more of the following effects can be obtained.
- (a) According to the current embodiment, the TiN film having an oxidation resistance greater than that of the Ni film is formed as the lowermost layer of the metal film, that is, the layer (interfacial surface) between the Ni film and the TiO2 film. Since the TiN film has an oxidation resistance greater than that of the Ni film, for example, when the Ni film is formed by a CVD method or the
wafer 200 on which the metal film is formed is heated to about 400° C. to perform an annealing treatment, it can be prevented that the Ni film is oxidized by an oxygen component permeated from the TiO2 film into the Ni film through an interfacial surface therebetween. Particularly, in the current embodiment, the TiN film is formed to have a thickness of 0.2 nm or greater in the TiN film-forming process S5. Thus, the TiN film formed between the Ni film and the TiO2 film can be surely constituted by one or more continuous layers, and thus the Ni film and the TiO2 film can be prevented from directly making contact with each other and oxidation of the Ni film can be effectively suppressed. Hence, oxidation of the metal film can be suppressed, and an increase of equivalent oxide thickness (EOT) can be prevented. - (b) In addition, according to the current embodiment, the TiN film (TiN cap layer) having an oxidation resistance greater than that of the Ni film is formed as the uppermost layer of the metal film, that is, the exposed surface layer of the metal film. Thus, permeation of oxygen from the atmosphere to the Ni film through the exposed surface of the metal film can be prevented, and thus oxidation of the Ni film can be suppressed. For example, when the
wafer 200 on which the metal film is exposed is carried for the next process, it can be prevented that the Ni film is oxidized at room temperature by oxygen permeated into the Ni film from the atmosphere through the exposed surface of the metal film. Particularly, according to the current embodiment, in the TiN cap forming process S12, the TiN film is formed to have a thickness of 0.2 nm to 50 nm, preferably, 1 nm to 10 nm, and thus the TiN film covering the surface of the Ni film can be surely constituted by one or more continuously layers. Therefore, the Ni film can be prevented from making direct contact with the atmosphere, and thus oxidation of the Ni film can be effectively suppressed. Hence, oxidation of the metal film can be suppressed, and an increase of EOT can be prevented. - (c) In addition, according to the current embodiment, the second metal film is formed of Ni (different from the first metal film in material) having a work function greater than 4.8 eV. Although the work function of TiN used to form the first metal film is estimated to be 4.6 eV, the work function of Ni is 5.15 eV as shown in
FIG. 10 . Thus, the effective work function of the entire metal film having a stacked structure constituted by the TiN film and the Ni film can be close to the work function of the Ni film (about 5.15 eV). Particularly, according to the current embodiment, the thickness of the Ni film formed in the Ni film-forming process S8 is greater than the thickness of the TiN film formed in the TiN film-forming process S5. Thus, the effect of the work function of the thicker Ni film is increased, and thus the effective work function of the entire work function of the metal film having a stacked structure constituted by the TiN film and the Ni film can be closer to the work function of the Ni film (about 5.15 eV). Therefore, when the metal film is used as a capacitor electrode, a leak current of a capacitor part can be reduced. - For example, if a metal film as shown in
FIG. 5A orFIG. 6A is formed by performing the TiN film-forming process S5 and the Ni film-forming process S8 once in a manner such that a TiN film is formed to have a thickness ranging from 0.2 nm to 4 nm in the TiN film-forming process S5 and a thicker Ni film is formed to have a thickness ranging from 0.5 nm to 10 nm, preferably, 4 nm to 5 nm in the Ni film-forming process S8, the effect of the work function of the thicker Ni film is high so that the effective work function of the entire metal film can approach about 5.0 eV. For example, when a metal film as shown inFIG. 5B orFIG. 6B is formed by setting the TiN film-forming process S5 and the Ni film-forming process S8 as one cycle and performing the cycle a plurality of times, the effective work function of the entire metal film can be adjusted to a desired value. That is, in this case, since the work functions of TiN films and Ni films are affected by each other, the effective work function of the entire metal film can be adjusted to a desired value between 4.6 eV and 5.0 eV by adjusting a thickness ratio of the TiN films and the Ni films. In either case, if the thickness of the TiN film formed in the TiN film-forming process S5 is greater than 4 nm, the effective work function of the entire metal film may be decreased to be close to the work function (4.6 eV) of the TiN film. -
FIG. 7 is a schematic view illustrating the energy level of a conventional capacitor electrode constituted by a single layer of TiN film. The leak current of a capacitor structure (metal-insulator-metal (MIM) structure), in which a capacitor insulating film (for example, a TiO2 film) is disposed between TiN films, is determined mainly by the work function of capacitor electrodes and the band offset (conduction band offset) of the conduction band side of the capacitor insulating film. Since a voltage of ±1 V is generally applied between capacitor electrodes, it is preferable that a conduction band offset is greater than 1.0 eV. In addition, since the work function of TiN is about 4.6 eV, if a TiO2 film is used as a capacitor insulating film, a conduction band offset of only about 1.0 eV may be ensured, and thus leak current may be increased. - However, if the metal film of the current embodiment is used as a capacitor electrode, the leak current of an MIM structure can be largely reduced.
FIG. 8 is a schematic view illustrating the energy levels of a metal film formed by performing the TiN film-forming process S5 and the Ni film-forming process S8 once. In this case, as described above, the work function of the metal film having a structure in which a TiN film and a Ni film are stacked can approach almost the same level (for example, 5. 0 eV) as the work function of the Ni film (about 5.15 eV). Therefore, if a TiO2 film is used as an insulating film, a conduction band offset of about 1.4 eV can be ensured, and thus leak current can be largely reduced. In addition,FIG. 9 is a schematic view illustrating the energy levels of a metal film formed by setting the TiN film-forming process S5 and the Ni film-forming process S8 as one cycle and performing the cycle a plurality of times. In this case, as described above, the work function of the metal film having a structure in which TiN films and Ni films are stacked can be adjusted to a desired value (for example, 4.8 eV) in the range of, for example, 4.6 eV to 5.0 eV. Therefore, if a TiO2 film is used as an insulating film, a conduction band offset can be set to a desired value (for example, 1.2 eV) in the range of 1.0 eV to 1.4 eV, and thus leak current can be effectively reduced. - (d) In addition, according to the current embodiment, a second metal film having a work function greater than 4.8 eV is formed by using a Ni film which is a metal film (non-noble metal film), instead of using an expensive noble metal film such as an Au, Ag, Pt, Pd, Rh, Ir, Ru, or Os film. In this way, manufacturing costs of semiconductor devices can be reduced.
- (e) In addition, according to the current embodiment, in a metal film having a stacked structure of a TiN film and a Ni film, the Ni film is formed by a CVD method. Therefore, the total film-forming rate of the metal film can be increased as compared with the case of using only an ALD method, and the throughput can be improved.
- In the above-described embodiment, a liquid source filled in the bubbler is vaporized by bubbling. However, the present invention is not limited thereto. For example, the liquid source may be vaporized by using a vaporizer instead of using the bubbler.
- Furthermore, in the above-described embodiment, TiCl4 is used as a Ti source in the TiN film-forming process S5. However, the present invention is not limited thereto. For example, a Ti source such as TDMAT (tetrakis(dimethylamino)titanium: Ti[N(CH3)2]4) may be used instead of TiCl4.
- Furthermore, in the above-described embodiment, a TiO2 film having a high permittivity is used as an insulating film. However, the present invention is not limited thereto. For example, the present invention can be applied to the case of using another insulating film or a high permittivity insulating film such as a hafnium oxide (HfO2) film, a zirconium oxide (ZrO2) film, a niobium oxide (Nb2O5) film, a tantalum oxide (Ta2O5) film, a hafnium oxide film doped with aluminum (HfAlO film), a zirconium oxide film doped with aluminum (ZrAlO film), a strontium titanate (SrTiO) film, a barium strontium titanate (BaSrTiO) film, and a lead zirconate titanate (PZT) film.
- Furthermore, in the above-described embodiment, a TiN film is used as a first metal film. However, the present invention is not limited thereto. For example, the present invention can be properly applied to the case where another film, such as a tantalum nitride (TaN) film, a titanium aluminum nitride (TiAlN) film, or tantalum aluminum nitride (TaAlN) film, is used as a first metal film. All the TaN film, the TiAlN film, and the TaAlN film have an oxidation resistance greater than that of a second metal film (Ni film). Furthermore, all the TaN film, the TiAlN film, and the TaAlN film have an oxidation resistance greater than that of a TiN film and can be usefully used as an oxidation barrier film. The TaN film is a conductive metal nitride film, the TiAlN film is a conductive composite metal film and the TaAlN film is a conductive composite metal film.
- Furthermore, in the above-described embodiment, a Ni film is used as a second metal film. However, the present invention is not limited thereto. For example, the present invention can be properly applied to the case where a non-noble metal film having a work function greater than 4.8 eV, such as a beryllium (Be) film, a carbon (C) film, a cobalt (Co), a selenium (Se) film, a tellurium (Te) film, or a rhenium (Re) film, is used as a second metal film. All the listed films are conductive elemental metal films.
FIG. 10 is a table illustrating a group of metals having work functions higher than 4.8 eV which can be used for forming a second metal film. - Hereinafter, examples 1 and 2 of the present invention will be described together with a conventional example and a comparative example with reference to
FIG. 12 toFIG. 16 . -
FIG. 12 is a schematic view for explaining a stacked structure of the example 1 (sample B) of the present invention together with a stacked structure of the conventional example (sample A) and a stacked structure of the comparative example (sample C). - In addition,
FIG. 11 is a flowchart for explaining processes of forming the sample A (conventional example), the sample B (example 1), and the sample C (comparative example) that are illustrated inFIG. 12 . - As shown in
FIG. 11 , to make the sample B (example 1), first, a surface treatment (cleaning) was performed to a silicon substrate (Si-sub) by using hydrogen fluoride (HF) (HF treatment). Next, a TiN film was formed on the silicon substrate as a bottom electrode (bottom metal deposition). Next, a HfO2 film doped with Al (HfAlO film) was formed on the TiN film as a capacitor insulating film (High-k film) (high-k deposition). Here, the ratio of Hf and Al included in the capacitor insulating film was set to be 19:1. Then, a post deposition annealing (PDA) was performed at 700° C., and then a process similar to the predetermined-time executing process S9 of the above-described embodiment was performed by using the substrate processing apparatus of the above-described embodiment so as to form a stacked structure (Ni/TiN-laminate structure) in which a plurality of TiN films and a plurality of Ni films were alternately stacked (top metal deposition). In the case of the sample B, the TiN film was first formed when forming the stacked structure (TiN start), and the stacked structure was formed in a manner such that the TiN film was formed between the Ni film and the HfAlO film. Here, the thicknesses of the TiN film and the Ni film were set to 1 nm, respectively, and the execution number of the predetermined-time executing process S9 was set to five so that the thickness of the stacked structure can be 10 nm. Then, a process similar to the TiN cap film-forming process S12 of the above-described embodiment was performed to form a TiN film (TiN cap film) having a thickness of 50 nm on the stacked structure of the TiN films and the Ni films (TiN deposition). In this way, a metal film (a stacked film constituted by the stacked structure of the TiN films and the Ni films, and the TiN cap film formed on the stacked structure) was formed as a top electrode. Then, a gate structure was patterned by photolithography (gate patterning), and after a forming gas annealing (FGA) treatment was performed at 400° C., an Al film was formed on the backside of the silicon substrate (backside Al deposition). - The sample C (comparative example) was prepared by forming a stacked structure (Ni/TiN-laminate structure) in which Ni films and TiN films were alternately stacked on a capacitor insulating film (top metal deposition). In the case of the sample C, the Ni film was first formed when forming the stacked structure (Ni start), and the stacked structure was formed in a manner such that the Ni film made direct contact with a HfAlO film. Other film-forming flows and conditions were set to be equal to those of the sample B.
- The sample A (conventional example) was prepared by forming a one-layer TiN film on a capacitor insulating film as a top electrode (TiN), instead of forming a stacked structure (Ni/TiN-laminate structure) in which Ni films and TiN films were alternately stacked on the capacitor insulating film. Furthermore, in the sample A, a TiN cap film having a thickness of 50 nm was not formed. Other film-forming flows and conditions were set to be equal to those of the sample B.
-
FIG. 13 is a graph illustrating the equivalent oxide thicknesses (EOTs) of the sample A (conventional example), the sample B (example 1), and the sample C (comparative example) illustrated inFIG. 12 . InFIG. 13 , the vertical axis denotes EOT (nm), and the horizontal axis denotes the samples. Referring toFIG. 13 , the EOT of the sample B (example 1) is 0.80 nm or less, which is almost not increased as compared with the EOT of the sample A (conventional example) in which a single layer of TiN having a high oxidation resistance is formed. However, the EOT of the sample C (comparative example), in which the stacked structure is formed in a manner such that a Ni film makes direct contact with the HfAlO film, is increased to 1.40 nm. This may be because the Ni film is oxidized by an oxygen component included in the HfAlO film. That is, like in the case of the sample B, if formation of a stacked structure is started from formation of a TiN film (TiN start) to dispose the TiN film between a Ni film and a HfAlO film, oxidation of the Ni film can be effectively suppressed. -
FIG. 14 is a graph illustrating relationships between leak current densities (Jg) and EOTs of the sample A (conventional example), the sample B (example 1), and the sample C (comparative example) illustrated inFIG. 12 . InFIG. 14 , the vertical axis denotes leak current density (Jg, A/cm2) when a voltage of −1 V is applied between top and bottom electrodes, and the horizontal axis denotes EOT (nm). Furthermore, inFIG. 14 , the symbol ♦ denotes the sample A (conventional example), the symbol ▴ denotes the sample B (example 1), and the symbol ⋄ denotes the sample C (comparative example). Referring toFIG. 14 , as compared with the sample A (symbol ♦), the EOT of the sample B (symbol ▴) is almost not increased and the leak current density (Jg) of the sample B is decreased by one digit. In addition, as compared with the sample A (symbol ♦), the leak current density (Jg) of the sample C (symbol ⋄) is decreased by one digit, but the EOT of the sample C (symbol ⋄) is largely increased. That is, like in the case of the sample B, if a TiN film is disposed between a Ni film and a HfAlO film, an increase of EOT can be suppressed, and along with this, leak current can be decreased. -
FIG. 15 is a graph illustrating relationships between leak current densities (Jg) and applied voltages of the sample A (conventional example), the sample B (example 1), and the sample C (comparative example) illustrated inFIG. 12 . InFIG. 15 , the vertical axis denotes leak current density (Jg, A/cm2), and the horizontal axis denotes voltage applied between top and bottom electrodes. Furthermore, inFIG. 15 , the dashed-dotted line denotes the sample A (conventional example), the solid line denotes the sample B (example 1), and the dashed line denotes the sample C (comparative example). Referring toFIG. 15 , in a general range (±1 V) of voltage applied between capacitor electrodes, the leak current densities (Jg) of the sample B (solid line) and the sample C (dashed line) are smaller than the leak current density (Jg) of the sample A (convention example). That is, like in the case of the sample B, if a stacked structure of TiN films and Ni films is formed, leak current can be decreased. -
FIG. 16A is a schematic view illustrating the stacked structure of an example 2 (sample D) of the present invention. In the sample D, a metal film was formed as a gate electrode by stacking a one-layer TiN film and a one-layer Ni film on a SiO2 film functioning as a gate insulating film. The TiN film was formed to be disposed between the Ni film and the SiO2 film. In addition, while varying the thickness of the TiN film to 0.2 nm, 1 nm, 2 nm, 3 nm, 4 nm, 5 nm, and 10 nm, a plurality of samples having different thickness TiN films were prepared. The thickness of the Ni film was set to 20 nm. -
FIG. 16B is a graph illustrating a relationship between the work function of the metal film and the thickness of the TiN film of the sample D together with those of the sample B and sample C. InFIG. 16B , the vertical axis denotes the work function (eV) of metal films, and the horizontal axis denotes the thickness (nm) of the TiN film of the sample D (example 2). InFIG. 16B , the symbol □ denotes the work function of the metal film of the sample D, the solid line denotes the work function of the metal film of the sample C, and the dashed line denotes the work function of the metal film of the sample B. Referring toFIG. 16B , in the range where the thickness of the TiN film of the sample D is 4 nm or less, the effective work function of the entire metal film having a stacked structure of the TiN film and the Ni film can approach the work function of the Ni film (about 5.15 eV). However, when the thickness of the TiN film is greater than 4 nm, since the effect of the work function of TiN increases, the effective work function of the entire metal film is decreased. Therefore, it is preferable that the thickness of the TiN film is 4.0 nm or less. - Furthermore, in the above-described embodiments, an explanation has been given on the case of performing a film-forming process using a single-wafer type substrate processing apparatus configured to process a substrate at a time. However, the present invention is not limited thereto. For example, a batch type vertical apparatus configured to process a plurality of substrates at a time may be used as a substrate processing apparatus to perform a substrate processing process.
-
FIG. 17A andFIG. 17B are schematic views illustrating avertical process furnace 302 of a vertical apparatus that can be suitably used according to an embodiment of the present invention, in whichFIG. 17A is a vertical sectional view of theprocess furnace 302, andFIG. 17B is a sectional view of theprocess furnace 302 taken along line A-A ofFIG. 17A . - As shown in
FIG. 17A , theprocess furnace 302 includes aheater 307 as a heating unit (heating mechanism). Theheater 307 has a cylindrical shape and is supported on a holding plate such as a heater base so that theheater 307 can be vertically fixed. - Inside the
heater 307, aprocess tube 303 is installed concentrically with theheater 307 as a reaction tube. Theprocess tube 303 is made of a heat-resistant material such as quartz (SiO2) and silicon carbide (SiC) and has a cylindrical shape with a closed top side and an opened bottom side. In the hollow part of theprocess tube 303, aprocess chamber 301 is formed, which is configured to accommodate substrates such aswafers 200 in a state where thewafers 200 are horizontally positioned and vertically arranged in multiple stages in a boat 317 (described later). - At the lower side of the
process tube 303, a manifold 309 is installed concentrically with theprocess tube 303. The manifold 309 is made of a material such as stainless steel and has a cylindrical shape with opened top and bottom sides. The manifold 309 is engaged with theprocess tube 303 and installed to support theprocess tube 303. Between the manifold 309 and theprocess tube 303, an O-ring 320 a is installed as a seal member. The manifold 309 is supported by the heater base such that theprocess tube 303 can be vertically fixed. Theprocess tube 303 and the manifold 309 constitute a reaction vessel. - A
first nozzle 333 a as a first gas introducing part, and asecond nozzle 333 b as a second gas introducing part are connected to the manifold 309 in a manner such that the first andsecond nozzles manifold 309. Each of the first andsecond nozzles process tube 303 and thewafers 200 along the inner wall of theprocess tube 303 from the lower side to the upper side in the arranged direction of thewafers 200. In the lateral sides of the vertical parts of the first andsecond nozzles - The same gas supply systems as those explained in the previous embodiment are connected to the first and
second nozzles first nozzle 333 a, and the reaction gas supply system is connected to thesecond nozzle 333 b. That is, in the current embodiment, source gases (the first source gas and the second source gas) are supplied through a nozzle different from a nozzle used to supply a reaction gas. Alternatively, the first source gas and the source gas may be supplied through different nozzles. - At the
manifold 309, anexhaust pipe 331 is installed to exhaust the inside atmosphere of theprocess chamber 301. A vacuum exhaust device such as avacuum pump 346 is connected to theexhaust pipe 331 through a pressure detector such apressure sensor 345 and a pressure regulator such as an auto pressure controller (APC)valve 342, and based on pressure information detected by thepressure sensor 345, theAPC valve 342 is controlled so that the inside of theprocess chamber 301 can be vacuum-evacuated to a predetermined pressure (vacuum degree). TheAPC valve 342 is an on-off valve configured to be opened and closed to start and stop vacuum evacuation of the inside of theprocess chamber 301, and configured to be adjusted in valve opening degree for adjusting the inside pressure of theprocess chamber 301. - At the lower side of the manifold 309, a
seal cap 319 is installed as a furnace port cover capable of hermetically closing the opened bottom side of themanifold 309. Theseal cap 319 is configured to be brought into contact with the manifold 309 in a vertical direction from the bottom side of themanifold 309. Theseal cap 319 is made of a metal such as stainless steel and has a circular disk shape. On the top surface of theseal cap 319, an O-ring 320 b is installed as a seal member configured to make contact with the bottom side of themanifold 309. At a side of theseal cap 319 opposite to theprocess chamber 301, arotary mechanism 367 is installed to rotate the boat 317 (described later). Arotation shaft 355 of therotary mechanism 367 is inserted through theseal cap 319 and is connected to theboat 317, so as to rotate thewafers 200 by rotating theboat 317. Theseal cap 319 is configured to be vertically moved by aboat elevator 315 which is disposed at the outside of theprocess tube 303 as an elevating mechanism, and by this, theboat 317 can be loaded into and out of theprocess chamber 301. - The
boat 317 which is a substrate holding tool is made of a heat-resistant material such as quartz or silicon carbide and is configured to hold a plurality ofwafers 200 in a state where thewafers 200 are horizontally positioned and arranged in multiple stages with the centers of thewafers 200 being aligned. At the lower part of theboat 317, an insulatingmember 318 made of a heat-resistant material such as quartz or silicon carbide is installed to prevent heat transfer from theheater 307 to theseal cap 319. In theprocess tube 303, atemperature sensor 363 is installed as a temperature detector, and based on temperature information detected by thetemperature sensor 363, power supplied to theheater 307 is controlled to obtain a desired temperature distribution in theprocess chamber 301. Like thefirst nozzle 333 a and thesecond nozzle 333 b, thetemperature sensor 363 is installed along the inner wall of theprocess tube 303. - A
controller 380 which is a controller (control part) is configured to control operations of parts such as theAPC valve 342, theheater 307, thetemperature sensor 363, thevacuum pump 346, therotary mechanism 367, theboat elevator 315, the valves va1 to va5, vb1 to vb5, vc1 to vc3, vd1 and vd2, and ve1 to ve3, and theMFCs - Next, an explanation will be given on a substrate processing process which is one of semiconductor device manufacturing processes for forming a thin film on a
wafer 200 by a CVD method using theprocess furnace 302 of the vertical apparatus. In the following description, each part of the vertical apparatus is controlled by thecontroller 380. - A plurality of
wafers 200 are charged into the boat 317 (wafer charging). Then, as shown inFIG. 17A , theboat 317 in which the plurality ofwafers 200 are held is lifted and loaded into theprocess chamber 301 by the boat elevator 315 (boat loading). In this state, the bottom side of the manifold 309 is sealed by theseal cap 319 with the O-ring 320 b being disposed therebetween. - The inside of the
process chamber 301 is vacuum-evacuated to a desired pressure (vacuum degree) by thevacuum pump 346. At this time, the inside pressure of theprocess chamber 301 is measured by thepressure sensor 345, and based on the measured pressure, theAPC valve 342 is feedback-controlled. In addition, the inside of theprocess chamber 301 is heated to a desired temperature by theheater 307. At this time, so as to obtain a desired temperature distribution in theprocess chamber 301, power to theheater 307 is feedback-controlled based on temperature information detected by thetemperature sensor 363. Then, therotary mechanism 367 rotates theboat 317 to rotate thewafers 200. - Then, according to a sequence similar to the sequence of the TiN film-forming process S5 to the TiN cap film-forming process S12, metal films having a stacked structure constituted by a TiN film and a Ni film are formed on TiO2 films previously formed on the
wafers 200, and then TiN films (TiN cap films) having a predetermined thickness are formed on the metal films. Thereafter, according to a sequence similar to the remaining gas removing process S13, a remaining gas removing process is performed. - After that, the
boat elevator 315 lowers theseal cap 319 to open the bottom side of the manifold 309 and unload theboat 317 from theprocess tube 303 through the opened bottom side of the manifold 309 in a state where thewafers 200 on which the metal films and the TiN cap films having predetermined thicknesses are formed are held in the boat 317 (boat unloading). Thereafter, the processedwafers 200 are discharged from the boat 317 (wafer discharging). - Although the vertical apparatus is used in the current embodiment, processes similar to the substrate processing processes of the above-described embodiment can be performed to obtain similar effects.
- In the above-described embodiments, an explanation has been given on the case where a TiN film and a Ni film are formed in the same process chamber. However, the present invention is not limited thereto. For example, a TiN film and a Ni film may be formed in different process chambers. In that case, as shown in
FIG. 18 , a substrate processing apparatus (cluster apparatus), such as a multi-chamber type substrate processing system including a plurality of process chambers, may be used. Hereinafter, an explanation will be given on an exemplary case where a TiN film and a Ni film are formed in different process chambers of the cluster apparatus. In the cluster apparatus of the current embodiment, Front Opening Unified Pods (FOUPs, hereinafter referred to as pods) 1 are used as wafer carrying carriers (substrate containers) configured to carrywafers 200. - As shown in
FIG. 18 , thecluster apparatus 10 includes a first wafer transfer chamber 11 (hereinafter referred to as a negative pressure transfer chamber 11) as a transfer module (carrying chamber) configured to endure a pressure (negative pressure) lower than atmospheric pressure, and when viewed from the top, a case 12 (hereinafter referred to as a negative pressure transfer chamber case 12) of the negativepressure transfer chamber 11 has a heptagonal box shape with closed top and bottom sides. The negative pressuretransfer chamber case 12 is configured as a carrying vessel (airtight vessel). At the center part of the negativepressure transfer chamber 11, a wafer transfer machine 13 (hereinafter referred to as a negative pressure transfer machine 13) is installed as a carrying robot configured to transfer awafer 200 under a negative pressure condition. - As loadlock modules (loadlock chambers), a carrying-in preliminary chamber 14 (hereinafter referred to as a carrying-in chamber 14) and a carrying-out preliminary chamber 15 (hereinafter referred as a carrying-out chamber 15) are closely disposed and connected to the biggest sidewall (front wall) of the seven sidewalls of the negative pressure
transfer chamber case 12. When viewed from the top, each of a case of the carrying-inchamber 14 and a case of the carrying-out chamber 15 is formed in an approximately rhombic shape with closed top and bottom sides and is configured as a loadlock chamber capable of enduring a negative pressure condition. - A second wafer transfer chamber 16 (hereinafter referred to as a positive pressure transfer chamber 16), which is a front end module configured to be kept at atmospheric pressure or higher (hereinafter referred to as a positive pressure), is connected to sides of the carrying-in
chamber 14 and the carrying-out chamber 15 opposite to the negativepressure transfer chamber 11, and when viewed from the top, a case of the positivepressure transfer chamber 16 has a horizontally elongated rectangular shape with closed top and bottom sides. Between the carrying-inchamber 14 and the positivepressure transfer chamber 16, agate valve 17A is installed, and between the carrying-inchamber 14 and the negativepressure transfer chamber 11, agate valve 17B is installed. Between the carrying-out chamber 15 and the positivepressure transfer chamber 16, agate valve 18A is installed, and between the carrying-out chamber 15 and the negativepressure transfer chamber 11, agate valve 18B is installed. In the positivepressure transfer chamber 16, a second wafer transfer machine 19 (hereinafter referred to as a positive pressure transfer machine 19) is installed as a carrying robot configured to transfer awafer 200 under a positive pressure condition. The positivepressure transfer machine 19 is configured to be moved upward and downward by an elevator installed at the positivepressure transfer chamber 16, and is also configured to reciprocate left and right by a linear actuator. At the left end part of the positivepressure transfer chamber 16, anotch aligning device 20 is installed. - At the front wall of the positive
pressure transfer chamber 16, threewafer carrying entrances wafers 200 can be carried into and out of the positivepressure transfer chamber 16 through the wafer carrying entrances 21, 22, and 23.Pod openers 24 are installed at the wafer carrying entrances 21, 22, and 23, respectively. Each of thepod openers 24 includes astage 25 on which apod 1 can be placed, and a cap attachment/detachment mechanism 26 configured to attach/detach a cap to/from apod 1 placed on thestage 25. By attaching/detaching a cap to/from apod 1 placed on thestage 25 by using thepod opener 24, a wafer taking in/out entrance of thepod 1 can be closed or opened.Pods 1 are supplied to thestages 25 of thepod openers 24 and taken away from thestages 25 of thepod openers 24 by an in-process carrying device (rail guided vehicle, RGV). - As shown in
FIG. 18 , as processing modules, a first process unit 31 (TiN film-forming unit 31) and a second process unit 32 (Ni film-forming unit 32) are closely disposed and respectively connected to two sidewalls (rear walls) of the seven sidewalls of the negative pressuretransfer chamber case 12 opposite to the positivepressure transfer chamber 16. Thefirst process unit 31 and thesecond process unit 32 have a structure similar to the substrate processing apparatus of the above-described embodiment. A first source supply system and a reaction gas supply system are installed at thefirst process unit 31 but a second source supply system is not installed at thefirst process unit 31, and a second source supply system is installed at thesecond process unit 32 but a first source supply system and a reaction gas supply system are not installed at thesecond process unit 32. This is a difference from the above-described embodiment. - Between the
first process unit 31 and the negativepressure transfer chamber 11, agate valve 44 is installed. Between thesecond process unit 32 and the negativepressure transfer chamber 11, agate valve 118 is installed. In addition, as cooling stages, afirst cooling unit 35 and asecond cooling unit 36 are respectively connected to two sidewalls of the seven sidewalls of the negative pressuretransfer chamber case 12 that face the positivepressure transfer chamber 16, and each of the first andsecond cooling units wafer 200. - The
cluster apparatus 10 includes amain controller 37 for overall controlling of substrate processing flows. Themain controller 37 controls each part of thecluster apparatus 10. - Next, process that a metal film having a stacked structure constituted by a TiN film and a Ni film is formed on a TiO2 film previously formed on a
wafer 200, and then a TiN film (TiN cap film) having a predetermined thickness is formed on the metal film will now be explained. In the following description, each part of thecluster apparatus 10 is controlled by themain controller 37. - A cap of a
pod 1 placed on thestage 25 of thecluster apparatus 10 is detached by the cap attachment/detachment mechanism 26, and thus a wafer taking in/out entrance of thepod 1 is opened. After thepod 1 is opened, the positivepressure transfer machine 19 installed at the positivepressure transfer chamber 16 picks upwafers 200 one by one from thepod 1 through the wafer carrying entrance and carries thewafers 200 to the carrying-inchamber 14 where thewafers 200 are placed on a carrying-in chamber temporary stage. During this operation, thegate valve 17A disposed at a side of the carrying-inchamber 14 facing the positivepressure transfer chamber 16 is in an opened state; thegate valve 17B disposed at the other side of the carrying-inchamber 14 facing the negativepressure transfer chamber 11 is in a closed state; and the inside of the negativepressure transfer chamber 11 is kept at, for example, 100 Pa. - The side of the carrying-in
chamber 14 facing the positivepressure transfer chamber 16 is closed by thegate valve 17A, and the carrying-inchamber 14 is exhausted to a negative pressure by an exhaust device. When the inside pressure of the carrying-inchamber 14 is reduced to a preset pressure, thegate valve 17B disposed at the other side of the carrying-inchamber 14 facing the negativepressure transfer chamber 11 is opened. Next, the negativepressure transfer machine 13 of the negativepressure transfer chamber 11 picks up thewafers 200 one by one from the carrying-in chamber temporary stage and carries thewafers 200 into the negativepressure transfer chamber 11. Thereafter, thegate valve 17B disposed at the other side of the carrying-inchamber 14 facing the negativepressure transfer chamber 11 is closed. - Subsequently, the
gate valve 44 of thefirst process unit 31 is opened, and the negativepressure transfer machine 13 loads thewafer 200 into a process chamber of the first process unit 31 (wafer loading). When thewafer 200 is loaded into the process chamber of thefirst process unit 31, since the carrying-inchamber 14 and the negativepressure transfer chamber 11 are previously vacuum-evacuated, permeation of oxygen or moisture into the process chamber of thefirst process unit 31 can be surely prevented. Then, according to a sequence similar to the sequence of the pressure adjusting process S3 to the TiN film-forming process S5 of the above-described embodiment, a TiN film is formed on a TiO2 film previously formed on thewafer 200. After that, in the reverse sequence to the above-described sequence, thewafer 200 on which the TiN film is formed to have a predetermined thickness is unloaded from the process chamber of thefirst process unit 31 to the negativepressure transfer chamber 11. - Subsequently, the
gate valve 118 of thesecond process unit 32 is opened, and the negativepressure transfer machine 13 loads thewafer 200 into a process chamber of the second process unit 32 (wafer loading). When thewafer 200 is loaded into the process chamber of thesecond process unit 32, since the carrying-inchamber 14 and thenegative pressure chamber 11 are previously vacuum-evacuated, permeation of oxygen or moisture into the process chamber of thesecond process unit 32 can be surely prevented. Then, according to a sequence similar to the sequence of the pressure adjusting process S6 to the Ni film-forming process S8 of the above-described embodiment, a Ni film is formed on the TiN film formed over thewafer 200 in thefirst process unit 31. After that, in the reverse sequence to the above-described sequence, thewafer 200 over which the Ni film is formed to have a predetermined thickness is unloaded from the process chamber of thesecond process unit 32 to the negativepressure transfer chamber 11. - Then, according to a sequence similar to the sequence of the predetermined-time executing process S9 of the above-described embodiment, the TiN film-forming process using the
first process unit 31 and the Ni film-forming process using thesecond process unit 32 are set as one cycle, and the cycle is performed predetermined times so as to form a metal film having a stacked structure of TiN film and Ni film on the TiO2 film previously formed on thewafer 200. - Subsequently, the
gate valve 44 of thefirst process unit 31 is opened, and the negativepressure transfer machine 13 loads thewafer 200 into the process chamber of the first process unit 31 (wafer loading). Then, according to a sequence similar to the sequence of the pressure adjusting process S10 to the TiN cap film-forming process S12, a TiN film (TiN cap film) having a predetermined thickness is formed on the metal film having a stacked structure of TiN film and Ni film. After that, in the reverse sequence to the above-described sequence, thewafer 200 over which the TiN film is formed to have a predetermined thickness is unloaded from the process chamber of thefirst process unit 31 to the negativepressure transfer chamber 11. - Thereafter, the side of the carrying-
out chamber 15 facing thenegative pressure chamber 11 is opened by thegate valve 18B, and the negativepressure transfer machine 13 carries thewafer 200 from thenegative pressure chamber 11 to the carrying-out chamber 15, and thewafer 200 is transferred to a carrying-out chamber temporary stage. For this, the side of the carrying-out chamber 15 facing the positivepressure transfer chamber 16 is previously closed by thegate valve 18A, and the carrying-out chamber 15 is exhausted to a negative pressure by an exhaust device. After the pressure of the carrying-out chamber 15 is decreased to a preset value, the side of the carrying-out chamber 15 facing thenegative pressure chamber 11 is opened by thegate valve 18B, and thewafer 200 is unloaded. After thewafer 200 is unloaded, thegate valve 18B is closed. - By repeating the above-described actions, twenty five
wafers 200 batch-loaded in thechamber 14 can be sequentially processed through the above-described processes. After the twenty fivewafers 200 are sequentially processed, the processedwafers 200 are collected on the temporary stage of the carrying-out chamber 15. - Thereafter, nitrogen gas is supplied into the carrying-
out chamber 15 which is kept at a negative pressure so as to adjust the inside pressure of the carrying-out chamber 15 to atmospheric pressure, and then the side of the carrying-out chamber 15 facing the positivepressure transfer chamber 16 is opened by thegate valve 18A. Next, a cap of anempty pod 1 placed on thestage 25 is opened by the cap attachment/detachment mechanism 26 of thepod opener 24. Subsequently, the positivepressure transfer machine 19 of the positivepressure transfer chamber 16 picks up thewafers 200 from the carrying-out chamber 15 to the positivepressure transfer chamber 16 and carries thewafers 200 into thepod 1 through thewafer carrying entrance 23 of the positivepressure transfer chamber 16. After the processed twenty fivewafers 200 are carried into thepod 1, the cap of thepod 1 is attached to the wafer taking in/out entrance of thepod 1 by the cap attachment/detachment mechanism 26 of thepod opener 24 so that thepod 1 is closed. - A process similar to the substrate processing process of the above-described embodiment can be performed by using the
cluster apparatus 10 of the current embodiment, and effects similar to those of the above-described embodiment can be obtained. In the case where process conditions (particularly, a process temperature) for forming a first metal film are different from process conditions (particularly, a process temperature) for forming a second metal film, the first and second metal films may be formed in different process chambers like in the current embodiment. - Furthermore, examples of a gate electrode forming process include: a gate first process in which a source/drain diffusion layer is formed by performing about 1000° C. annealing, that is, activation annealing (spike annealing) after a gate electrode is formed; and a gate last process in which such a source/drain diffusion layer is formed before a gate electrode is formed. In the case of a gate first process, a gate electrode is heated to about 1,000° C. during activation annealing, and thus the present invention may be unsuitable for a gate first process because a TiN film does not have oxidation resistance in a temperature region of about 1,000° C. However, in the case of a gate last process, a gate electrode is not heated to a temperature about 1,000° C., and a TiN film has oxidation resistance in temperature regions of processes that are performed after the gate electrode is formed. Thus, the present invention may be suitable for a gate last process. That is, the present invention can be suitably applied to the case where a gate electrode is formed through a gate last process. Furthermore, in a process of manufacturing a dynamic random access memory (DRAM), annealing is performed at about 400° C. under a H2-gas atmosphere after a capacitor electrode is formed. In a DRAM manufacturing process, a capacitor electrode is heated to about 400° C. at most, and in such a temperature condition, TiN has high oxidation resistance as compared with Ni. That is, the present invention can be suitably applied to the case where a capacitor electrode of a DRAM is manufactured.
- As described above, the present invention provides a semiconductor device including a metal film which can be formed with lower costs but have a necessary work function and oxidation resistance. In addition, according to the present invention, there are provided a method of manufacturing a semiconductor device and a substrate processing apparatus, which are designed to form a metal film having a necessary work function and oxidation resistance with lower costs.
- <Supplementary Note>
- The present invention also includes the following preferred embodiments.
- According to an embodiment of the present invention, there is provided a semiconductor device including: an insulating film disposed on a substrate; and a metal film disposed adjacent to the insulating film, wherein the metal film includes a stacked structure of a first metal film and a second metal film, an oxidation resistance of the first metal film is greater than that of the second metal film, the second metal film has a work function greater than 4.8 eV and is different from the first metal film in material, and the first metal film is disposed between the second metal film and the insulating film.
- Preferably, the metal film is disposed on the insulating film, and further includes the first metal film disposed on an outermost surface thereof.
- Preferably, the stacked structure is repeatedly stacked in the metal film.
- Preferably, a thickness of the first metal film ranges from 0.2 nm to 4 nm.
- Preferably, a thickness of the second metal film ranges from 0.5 nm to 10 nm.
- Preferably, a thickness of the second metal film ranges from 4 nm to 5 nm.
- Preferably, the second metal film is thicker than the first metal film.
- Preferably, the first metal film includes one of a titanium nitride film, a tantalum nitride film, a titanium aluminum nitride film, and a tantalum aluminum nitride film.
- Preferably, the second metal film includes a non-noble metal.
- Preferably, the second metal film includes at least one of a nickel film, a cobalt film, a beryllium film, a carbon film, a selenium film, a tellurium film and a rhenium film.
- Preferably, the insulating film includes a high permittivity film.
- Preferably, the insulating film includes at least one of a hafnium oxide film, a zirconium oxide film, a hafnium oxide film doped with an aluminum, a zirconium oxide film doped with the aluminum, a titanium oxide film, a niobium oxide film, a tantalum oxide film, a strontium titanate film, a barium strontium titanate film and a lead zirconate titanate film.
- According to another embodiment of the present invention, there is provided a method of manufacturing a semiconductor device, the method including: forming an insulating film on a substrate; and forming a metal film including a stacked structure of a first metal film and a second metal film adjacent to the insulating film, the first metal film being formed between the second metal film and the insulating film, wherein an oxidation resistance of the first metal film is greater than that of the second metal film, and the second metal film has a work function greater than 4.8 eV and is different from the first metal film in material.
- According to another embodiment of the present invention, there is provided a substrate processing apparatus including: a process chamber configured to process a substrate; a first process gas supply system configured to supply a first process gas into the process chamber to form a first metal film; a second process gas supply system configured to supply a second process gas into the process chamber to form a second metal film; and a controller configured to control the first process gas supply system and the second process gas supply system, wherein an oxidation resistance of the first metal film is greater than that of the second metal film, the second metal film has a work function greater than 4.8 eV and is different from the first metal film in material, and the controller controls the first process gas supply system and the second process gas supply system to form a metal film having a stacked structure of the first metal film and the second metal film adjacent to an insulating film disposed on the substrate by supplying the first process gas and the second process gas into the process chamber where the substrate is accommodated such that the first metal film is formed between the second metal film and the insulating film.
- According to another embodiment of the present invention, there is provided a substrate processing apparatus including: a first process chamber configured to process a substrate; a first process gas supply system configured to supply a first process gas into the first process chamber to form a first metal film; a second process chamber configured to process the substrate; a second process gas supply system configured to supply a second process gas into the second process chamber to form a second metal film; a carrying chamber disposed between the first process chamber and the second process chamber for carrying the substrate; a carrying robot installed in the carrying chamber to carry the substrate between the first process chamber and the second process chamber; and a controller configured to control the first process gas supply system, the second process gas supply system and the carrying robot, wherein an oxidation resistance of the first metal film is greater than that of the second metal film, the second metal film has a work function greater than 4.8 eV and is different from the first metal film in material, and the controller controls the first process gas supply system, the second process gas supply system and the carrying robot to form a metal film having a stacked structure of the first metal film and the second metal film adjacent to an insulating film disposed on the substrate by carrying the substrate into the first process chamber, supplying the first process gas into the first process chamber, carrying the substrate into the second process chamber, and supplying the second process gas into the process chamber such that the first metal film is formed between the second metal film and the insulating film.
Claims (14)
1. A semiconductor device comprising:
an insulating film disposed on a substrate; and
a metal film disposed adjacent to the insulating film,
wherein the metal film comprises a stacked structure of a first metal film and a second metal film,
an oxidation resistance of the first metal film is greater than that of the second metal film,
the second metal film has a work function greater than 4.8 eV and is different from the first metal film in material, and
the first metal film is disposed between the second metal film and the insulating film.
2. The semiconductor device of claim 1 , wherein the metal film is disposed on the insulating film, and further comprises the first metal film disposed on an outermost surface thereof.
3. The semiconductor device of claim 1 , wherein the stacked structure is repeatedly stacked in the metal film.
4. The semiconductor device of claim 1 , wherein a thickness of the first metal film ranges from 0.2 nm to 4 nm.
5. The semiconductor device of claim 1 , wherein a thickness of the second metal film ranges from 0.5 nm to 10 nm.
6. The semiconductor device of claim 1 , wherein a thickness of the second metal film ranges from 4 nm to 5 nm.
7. The semiconductor device of claim 1 , wherein the second metal film is thicker than the first metal film.
8. The semiconductor device of claim 1 , wherein the first metal film comprises one of a titanium nitride film, a tantalum nitride film, a titanium aluminum nitride film, and a tantalum aluminum nitride film.
9. The semiconductor device of claim 1 , wherein the second metal film comprises a non-noble metal.
10. The semiconductor device of claim 1 , wherein the second metal film comprises at least one of a nickel film, a cobalt film, a beryllium film, a carbon film, a selenium film, a tellurium film and a rhenium film.
11. The semiconductor device of claim 1 , wherein the insulating film comprises a high permittivity film.
12. The semiconductor device of claim 1 , wherein the insulating film comprises at least one of a hafnium oxide film, a zirconium oxide film, a hafnium oxide film doped with an aluminum, a zirconium oxide film doped with the aluminum, a titanium oxide film, a niobium oxide film, a tantalum oxide film, a strontium titanate film, a barium strontium titanate film and a lead zirconate titanate film.
13. A method of manufacturing a semiconductor device, the method comprising:
forming an insulating film on a substrate; and
forming a metal film comprising a stacked structure of a first metal film and a second metal film adjacent to the insulating film, the first metal film being formed between the second metal film and the insulating film,
wherein an oxidation resistance of the first metal film is greater than that of the second metal film, and
the second metal film has a work function greater than 4.8 eV and is different from the first metal film in material.
14. A substrate processing apparatus comprising:
a process chamber configured to process a substrate;
a first process gas supply system configured to supply a first process gas into the process chamber to form a first metal film;
a second process gas supply system configured to supply a second process gas into the process chamber to form a second metal film; and
a controller configured to control the first process gas supply system and the second process gas supply system,
wherein an oxidation resistance of the first metal film is greater than that of the second metal film,
the second metal film has a work function greater than 4.8 eV and is different from the first metal film in material, and
the controller controls the first process gas supply system and the second process gas supply system to form a metal film having a stacked structure of the first metal film and the second metal film adjacent to an insulating film disposed on the substrate by supplying the first process gas and the second process gas into the process chamber where the substrate is accommodated such that the first metal film is formed between the second metal film and the insulating film.
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US14/629,345 US9437704B2 (en) | 2010-01-07 | 2015-02-23 | Semiconductor device having electrode made of high work function material, method and apparatus for manufacturing the same |
US14/629,338 US9472637B2 (en) | 2010-01-07 | 2015-02-23 | Semiconductor device having electrode made of high work function material and method of manufacturing the same |
US15/228,840 US9653301B2 (en) | 2010-01-07 | 2016-08-04 | Semiconductor device having electrode made of high work function material, method and apparatus for manufacturing the same |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2010002256A JP5721952B2 (en) | 2010-01-07 | 2010-01-07 | Semiconductor device, semiconductor device manufacturing method, and substrate processing apparatus |
JP2010-002256 | 2010-01-07 |
Related Child Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US14/629,345 Continuation US9437704B2 (en) | 2010-01-07 | 2015-02-23 | Semiconductor device having electrode made of high work function material, method and apparatus for manufacturing the same |
US14/629,338 Continuation-In-Part US9472637B2 (en) | 2010-01-07 | 2015-02-23 | Semiconductor device having electrode made of high work function material and method of manufacturing the same |
Publications (1)
Publication Number | Publication Date |
---|---|
US20110163452A1 true US20110163452A1 (en) | 2011-07-07 |
Family
ID=44224230
Family Applications (3)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US12/984,018 Abandoned US20110163452A1 (en) | 2010-01-07 | 2011-01-04 | Semiconductor device, method of manufacturing semiconductor device, and substrate processing apparatus |
US14/629,345 Active US9437704B2 (en) | 2010-01-07 | 2015-02-23 | Semiconductor device having electrode made of high work function material, method and apparatus for manufacturing the same |
US15/228,840 Active US9653301B2 (en) | 2010-01-07 | 2016-08-04 | Semiconductor device having electrode made of high work function material, method and apparatus for manufacturing the same |
Family Applications After (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US14/629,345 Active US9437704B2 (en) | 2010-01-07 | 2015-02-23 | Semiconductor device having electrode made of high work function material, method and apparatus for manufacturing the same |
US15/228,840 Active US9653301B2 (en) | 2010-01-07 | 2016-08-04 | Semiconductor device having electrode made of high work function material, method and apparatus for manufacturing the same |
Country Status (3)
Country | Link |
---|---|
US (3) | US20110163452A1 (en) |
JP (1) | JP5721952B2 (en) |
TW (1) | TWI427791B (en) |
Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20130075800A1 (en) * | 2011-09-26 | 2013-03-28 | Hitachi Kokusai Electric Inc. | Semiconductor device manufacturing method, semiconductor device and substrate processing apparatus |
US20140287593A1 (en) * | 2013-03-21 | 2014-09-25 | Applied Materials, Inc. | High throughput multi-layer stack deposition |
FR3005201A1 (en) * | 2013-04-24 | 2014-10-31 | St Microelectronics Crolles 2 | METHOD FOR MAKING A METAL GRID MOS TRANSISTOR, ESPECIALLY A PMOS TRANSISTOR, AND CORRESPONDING INTEGRATED CIRCUIT |
CN104851780A (en) * | 2014-02-19 | 2015-08-19 | 朗姆研究公司 | Method and device for processing wafer-shaped articles |
US20150247238A1 (en) * | 2014-03-03 | 2015-09-03 | Lam Research Corporation | Rf cycle purging to reduce surface roughness in metal oxide and metal nitride films |
US9425039B2 (en) | 2014-03-26 | 2016-08-23 | Hitachi Kokusai Electric Inc. | Method of manufacturing semiconductor device, substrate processing apparatus and non-transitory computer-readable recording medium |
CN106201936A (en) * | 2012-01-09 | 2016-12-07 | 联发科技股份有限公司 | Access method and electronic installation for dynamic random access memory |
US20170110552A1 (en) * | 2015-10-20 | 2017-04-20 | Taiwan Semiconductor Manufacturing Co., Ltd. | Atomic layer deposition methods and structures thereof |
US20180082871A1 (en) * | 2016-09-22 | 2018-03-22 | Globalfoundries Inc. | Gas flow process control system and method using crystal microbalance(s) |
US20190096984A1 (en) * | 2017-09-28 | 2019-03-28 | Stmicroelectronics S.R.L. | High-voltage capacitor, system including the capacitor and method for manufacturing the capacitor |
US10950688B2 (en) * | 2019-02-21 | 2021-03-16 | Kemet Electronics Corporation | Packages for power modules with integrated passives |
US11004676B2 (en) | 2015-03-30 | 2021-05-11 | Kokusai Electric Corporation | Method for manufacturing semiconductor device, non-transitory computer-readable recording medium, and substrate processing apparatus |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP6086892B2 (en) | 2014-11-25 | 2017-03-01 | 株式会社日立国際電気 | Semiconductor device manufacturing method, substrate processing apparatus, and program |
US10170321B2 (en) | 2017-03-17 | 2019-01-01 | Applied Materials, Inc. | Aluminum content control of TiAIN films |
US9983118B1 (en) * | 2017-06-03 | 2018-05-29 | Himax Technologies Limited | Wafer holding apparatus |
US20230178342A1 (en) * | 2020-06-01 | 2023-06-08 | Lam Research Corporation | Mid-chamber flow optimizer |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6271133B1 (en) * | 1999-04-12 | 2001-08-07 | Chartered Semiconductor Manufacturing Ltd. | Optimized Co/Ti-salicide scheme for shallow junction deep sub-micron device fabrication |
US20040203229A1 (en) * | 2003-04-08 | 2004-10-14 | Sunfei Fang | Salicide formation method |
US20050082625A1 (en) * | 2002-04-11 | 2005-04-21 | Kim Byung-Hee | Methods of forming electronic devices including high-k dielectric layers and electrode barrier layers |
US20080076216A1 (en) * | 2006-09-25 | 2008-03-27 | Sangwoo Pae | Method to fabricate high-k/metal gate transistors using a double capping layer process |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3851752B2 (en) | 2000-03-27 | 2006-11-29 | 株式会社東芝 | Manufacturing method of semiconductor device |
US6861712B2 (en) * | 2003-01-15 | 2005-03-01 | Sharp Laboratories Of America, Inc. | MOSFET threshold voltage tuning with metal gate stack control |
US7473640B2 (en) | 2003-01-15 | 2009-01-06 | Sharp Laboratories Of America, Inc. | Reactive gate electrode conductive barrier |
JP2005244186A (en) * | 2004-02-23 | 2005-09-08 | Sharp Corp | Reactive gate electrode conductive barrier |
US7598545B2 (en) * | 2005-04-21 | 2009-10-06 | International Business Machines Corporation | Using metal/metal nitride bilayers as gate electrodes in self-aligned aggressively scaled CMOS devices |
JP2008028058A (en) * | 2006-07-20 | 2008-02-07 | Tokyo Electron Ltd | Method of manufacturing semiconductor device, apparatus for manufacturing semiconductor device, semiconductor device and storage medium |
JP5513767B2 (en) | 2008-06-25 | 2014-06-04 | 株式会社日立国際電気 | Semiconductor device manufacturing method, substrate processing method, substrate processing apparatus, and semiconductor device |
-
2010
- 2010-01-07 JP JP2010002256A patent/JP5721952B2/en active Active
- 2010-12-27 TW TW099145996A patent/TWI427791B/en active
-
2011
- 2011-01-04 US US12/984,018 patent/US20110163452A1/en not_active Abandoned
-
2015
- 2015-02-23 US US14/629,345 patent/US9437704B2/en active Active
-
2016
- 2016-08-04 US US15/228,840 patent/US9653301B2/en active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6271133B1 (en) * | 1999-04-12 | 2001-08-07 | Chartered Semiconductor Manufacturing Ltd. | Optimized Co/Ti-salicide scheme for shallow junction deep sub-micron device fabrication |
US20050082625A1 (en) * | 2002-04-11 | 2005-04-21 | Kim Byung-Hee | Methods of forming electronic devices including high-k dielectric layers and electrode barrier layers |
US20040203229A1 (en) * | 2003-04-08 | 2004-10-14 | Sunfei Fang | Salicide formation method |
US20080076216A1 (en) * | 2006-09-25 | 2008-03-27 | Sangwoo Pae | Method to fabricate high-k/metal gate transistors using a double capping layer process |
Cited By (23)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20130075800A1 (en) * | 2011-09-26 | 2013-03-28 | Hitachi Kokusai Electric Inc. | Semiconductor device manufacturing method, semiconductor device and substrate processing apparatus |
CN106201936A (en) * | 2012-01-09 | 2016-12-07 | 联发科技股份有限公司 | Access method and electronic installation for dynamic random access memory |
US20140287593A1 (en) * | 2013-03-21 | 2014-09-25 | Applied Materials, Inc. | High throughput multi-layer stack deposition |
FR3005201A1 (en) * | 2013-04-24 | 2014-10-31 | St Microelectronics Crolles 2 | METHOD FOR MAKING A METAL GRID MOS TRANSISTOR, ESPECIALLY A PMOS TRANSISTOR, AND CORRESPONDING INTEGRATED CIRCUIT |
US9257518B2 (en) | 2013-04-24 | 2016-02-09 | STMicrolectronics (Crolles 2) SAS | Method for producing a metal-gate MOS transistor, in particular a PMOS transistor, and corresponding integrated circuit |
CN104851780A (en) * | 2014-02-19 | 2015-08-19 | 朗姆研究公司 | Method and device for processing wafer-shaped articles |
US20150235876A1 (en) * | 2014-02-19 | 2015-08-20 | Lam Research Ag | Method and apparatus for processing wafer-shaped articles |
US9698029B2 (en) * | 2014-02-19 | 2017-07-04 | Lam Research Ag | Method and apparatus for processing wafer-shaped articles |
US20150247238A1 (en) * | 2014-03-03 | 2015-09-03 | Lam Research Corporation | Rf cycle purging to reduce surface roughness in metal oxide and metal nitride films |
US9425039B2 (en) | 2014-03-26 | 2016-08-23 | Hitachi Kokusai Electric Inc. | Method of manufacturing semiconductor device, substrate processing apparatus and non-transitory computer-readable recording medium |
US11004676B2 (en) | 2015-03-30 | 2021-05-11 | Kokusai Electric Corporation | Method for manufacturing semiconductor device, non-transitory computer-readable recording medium, and substrate processing apparatus |
US10923576B2 (en) * | 2015-10-20 | 2021-02-16 | Taiwan Semiconductor Manufacturing Co., Ltd. | Atomic layer deposition methods and structures thereof |
CN107017157A (en) * | 2015-10-20 | 2017-08-04 | 台湾积体电路制造股份有限公司 | Atomic layer deposition method and its structure |
US9972694B2 (en) * | 2015-10-20 | 2018-05-15 | Taiwan Semiconductor Manufacturing Company, Ltd. | Atomic layer deposition methods and structures thereof |
US20180261678A1 (en) * | 2015-10-20 | 2018-09-13 | Taiwan Semiconductor Manufacturing Co., Ltd. | Atomic layer deposition methods and structures thereof |
US20170110552A1 (en) * | 2015-10-20 | 2017-04-20 | Taiwan Semiconductor Manufacturing Co., Ltd. | Atomic layer deposition methods and structures thereof |
US10658488B2 (en) | 2015-10-20 | 2020-05-19 | Taiwan Semiconductor Manufacturing Co., Ltd. | Atomic layer deposition methods and structures thereof |
US20180082871A1 (en) * | 2016-09-22 | 2018-03-22 | Globalfoundries Inc. | Gas flow process control system and method using crystal microbalance(s) |
US10256126B2 (en) * | 2016-09-22 | 2019-04-09 | Globalfoundries Inc. | Gas flow process control system and method using crystal microbalance(s) |
US20190096984A1 (en) * | 2017-09-28 | 2019-03-28 | Stmicroelectronics S.R.L. | High-voltage capacitor, system including the capacitor and method for manufacturing the capacitor |
US10916622B2 (en) * | 2017-09-28 | 2021-02-09 | Stmicroelectronics S.R.L. | High-voltage capacitor, system including the capacitor and method for manufacturing the capacitor |
US11574996B2 (en) * | 2017-09-28 | 2023-02-07 | Stmicroelectronics S.R.L. | High-voltage capacitor, system including the capacitor and method for manufacturing the capacitor |
US10950688B2 (en) * | 2019-02-21 | 2021-03-16 | Kemet Electronics Corporation | Packages for power modules with integrated passives |
Also Published As
Publication number | Publication date |
---|---|
US9653301B2 (en) | 2017-05-16 |
JP5721952B2 (en) | 2015-05-20 |
JP2011142226A (en) | 2011-07-21 |
US9437704B2 (en) | 2016-09-06 |
TW201131773A (en) | 2011-09-16 |
TWI427791B (en) | 2014-02-21 |
US20160343573A1 (en) | 2016-11-24 |
US20150171180A1 (en) | 2015-06-18 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US9653301B2 (en) | Semiconductor device having electrode made of high work function material, method and apparatus for manufacturing the same | |
US9472637B2 (en) | Semiconductor device having electrode made of high work function material and method of manufacturing the same | |
US8404603B2 (en) | Method of manufacturing semiconductor device and substrate processing system | |
US8937022B2 (en) | Method of manufacturing semiconductor device, substrate processing method and substrate processing apparatus | |
US8492258B2 (en) | Method of manufacturing semiconductor device and substrate processing apparatus | |
US8685866B2 (en) | Method of manufacturing semiconductor device and substrate processing apparatus | |
US8741731B2 (en) | Method of manufacturing a semiconductor device | |
US8728935B2 (en) | Method of manufacturing semiconductor device, method of processing substrate and substrate processing apparatus | |
KR101097753B1 (en) | Manufacturing method of semiconductor device and substrate processing apparatus | |
US9190281B2 (en) | Method of manufacturing semiconductor device | |
JP5801916B2 (en) | Semiconductor device manufacturing method, substrate processing method, and substrate processing apparatus | |
JP5944549B2 (en) | Semiconductor device manufacturing method, substrate processing apparatus, and semiconductor device | |
JP2011066345A (en) | Method of manufacturing semiconductor device, and substrate processing system | |
JP2012064857A (en) | Semiconductor device manufacturing method and substrate processing apparatus | |
JP5174975B2 (en) | Semiconductor device manufacturing method, substrate processing method, and substrate processing apparatus | |
JP2009170711A (en) | Manufacturing method of semiconductor device, and substrate processing device |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: HITACHI KOKUSAI ELECTRIC INC., JAPAN Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:HORII, SADAYOSHI;OGAWA, ARITO;ITATANI, HIDEHARU;REEL/FRAME:025954/0141 Effective date: 20110112 |
|
STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION |