WO2007139041A1 - 金属化合物層の形成方法、半導体装置の製造方法及び金属化合物層の形成装置 - Google Patents
金属化合物層の形成方法、半導体装置の製造方法及び金属化合物層の形成装置 Download PDFInfo
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- WO2007139041A1 WO2007139041A1 PCT/JP2007/060745 JP2007060745W WO2007139041A1 WO 2007139041 A1 WO2007139041 A1 WO 2007139041A1 JP 2007060745 W JP2007060745 W JP 2007060745W WO 2007139041 A1 WO2007139041 A1 WO 2007139041A1
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- Prior art keywords
- metal compound
- forming
- compound layer
- source gas
- layer
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- 150000002736 metal compounds Chemical class 0.000 title claims abstract description 191
- 238000000034 method Methods 0.000 title claims abstract description 132
- 239000004065 semiconductor Substances 0.000 title claims abstract description 30
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 14
- 239000000758 substrate Substances 0.000 claims abstract description 261
- 229910052751 metal Inorganic materials 0.000 claims abstract description 89
- 239000002184 metal Substances 0.000 claims abstract description 88
- 239000002994 raw material Substances 0.000 claims abstract description 74
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 37
- 239000010703 silicon Substances 0.000 claims abstract description 34
- 239000000463 material Substances 0.000 claims abstract description 26
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 16
- 229910000577 Silicon-germanium Inorganic materials 0.000 claims abstract description 15
- LEVVHYCKPQWKOP-UHFFFAOYSA-N [Si].[Ge] Chemical compound [Si].[Ge] LEVVHYCKPQWKOP-UHFFFAOYSA-N 0.000 claims abstract description 14
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910021332 silicide Inorganic materials 0.000 claims description 275
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 claims description 273
- 230000015572 biosynthetic process Effects 0.000 claims description 128
- 239000013078 crystal Substances 0.000 claims description 81
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 229910005883 NiSi Inorganic materials 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 229910018999 CoSi2 Inorganic materials 0.000 claims 1
- 229940126062 Compound A Drugs 0.000 claims 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims 1
- 229910005877 NiSi3 Inorganic materials 0.000 claims 1
- 241001115903 Raphus cucullatus Species 0.000 claims 1
- 239000007789 gas Substances 0.000 description 198
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 129
- 239000012071 phase Substances 0.000 description 88
- 239000000203 mixture Substances 0.000 description 73
- 230000008569 process Effects 0.000 description 30
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 26
- 229920005591 polysilicon Polymers 0.000 description 26
- 238000000137 annealing Methods 0.000 description 21
- 238000000151 deposition Methods 0.000 description 17
- 238000000354 decomposition reaction Methods 0.000 description 16
- 239000012535 impurity Substances 0.000 description 14
- 238000010586 diagram Methods 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 12
- 238000005229 chemical vapour deposition Methods 0.000 description 10
- 230000005284 excitation Effects 0.000 description 10
- 230000008859 change Effects 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 239000012159 carrier gas Substances 0.000 description 8
- 230000008021 deposition Effects 0.000 description 8
- 238000005530 etching Methods 0.000 description 8
- 238000001179 sorption measurement Methods 0.000 description 7
- 230000007423 decrease Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 238000001465 metallisation Methods 0.000 description 6
- 238000005979 thermal decomposition reaction Methods 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 5
- -1 germanium metal compound Chemical class 0.000 description 5
- 230000007246 mechanism Effects 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 238000003795 desorption Methods 0.000 description 4
- 238000004544 sputter deposition Methods 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 229910021334 nickel silicide Inorganic materials 0.000 description 3
- RUFLMLWJRZAWLJ-UHFFFAOYSA-N nickel silicide Chemical compound [Ni]=[Si]=[Ni] RUFLMLWJRZAWLJ-UHFFFAOYSA-N 0.000 description 3
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 3
- 238000009751 slip forming Methods 0.000 description 3
- 229910021341 titanium silicide Inorganic materials 0.000 description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 3
- 238000007740 vapor deposition Methods 0.000 description 3
- 201000005569 Gout Diseases 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- ZXEYZECDXFPJRJ-UHFFFAOYSA-N $l^{3}-silane;platinum Chemical compound [SiH3].[Pt] ZXEYZECDXFPJRJ-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- BSYNRYMUTXBXSQ-UHFFFAOYSA-N Aspirin Chemical compound CC(=O)OC1=CC=CC=C1C(O)=O BSYNRYMUTXBXSQ-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910019001 CoSi Inorganic materials 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- 229910012990 NiSi2 Inorganic materials 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 235000018936 Vitellaria paradoxa Nutrition 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000002291 germanium compounds Chemical class 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000005468 ion implantation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- PEUPIGGLJVUNEU-UHFFFAOYSA-N nickel silicon Chemical group [Si].[Ni] PEUPIGGLJVUNEU-UHFFFAOYSA-N 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229910021339 platinum silicide Inorganic materials 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- XROWMBWRMNHXMF-UHFFFAOYSA-J titanium tetrafluoride Chemical compound [F-].[F-].[F-].[F-].[Ti+4] XROWMBWRMNHXMF-UHFFFAOYSA-J 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
- H01L29/66007—Multistep manufacturing processes
- H01L29/66075—Multistep manufacturing processes of devices having semiconductor bodies comprising group 14 or group 13/15 materials
- H01L29/66227—Multistep manufacturing processes of devices having semiconductor bodies comprising group 14 or group 13/15 materials the devices being controllable only by the electric current supplied or the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched, e.g. three-terminal devices
- H01L29/66409—Unipolar field-effect transistors
- H01L29/66477—Unipolar field-effect transistors with an insulated gate, i.e. MISFET
- H01L29/665—Unipolar field-effect transistors with an insulated gate, i.e. MISFET using self aligned silicidation, i.e. salicide
-
- 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
- C23C16/50—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 using electric discharges
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
- H01L21/28008—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
- H01L21/28035—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 silicon, e.g. polysilicon, with or without impurities
- H01L21/28044—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 silicon, e.g. polysilicon, with or without impurities the conductor comprising at least another non-silicon conductive layer
- H01L21/28052—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 silicon, e.g. polysilicon, with or without impurities the conductor comprising at least another non-silicon conductive layer the conductor comprising a silicide layer formed by the silicidation reaction of silicon with a metal layer
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
- H01L21/28008—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
- H01L21/28097—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 metallic silicide
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
- H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
- H01L21/285—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation
- H01L21/28506—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers
- H01L21/28512—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic Table
- H01L21/28518—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic Table the conductive layers comprising silicides
Definitions
- Metal compound layer forming method, semiconductor device manufacturing method, and metal compound layer forming device Metal compound layer forming method, semiconductor device manufacturing method, and metal compound layer forming device
- the present invention relates to a method and apparatus for forming a metal compound layer used in a semiconductor device such as an integrated circuit, and a method for manufacturing a semiconductor device.
- the present invention relates to a method and method for forming a metal compound layer used for a gate electrode. It is a technology related to equipment. Rice field
- Advanced CMO S complementary MO S
- the metal is bonded after the gate electrode material is deposited and after the source / drain regions are formed, and annealing is performed on the gate electrode material and the source Z drain region.
- a salicide technique is used in which only the metal deposited on the silicide is silicided, and then unreacted metal is removed by selective etching.
- N-type MOS FETs have a Si function of a mid cap (4.6 eV) or less, preferably 4.4 eV or less.
- a method for forming a metal compound layer having a large area with good uniformity and superior dominance is required.
- J. Va c. S ci. T echnol. B 1 9 (6), No ⁇ / ⁇ ec 2 0 0 1 L 2026 (hereinafter referred to as non-patent literature) uses a sputtering method on a polysilicon congruent pattern. After forming the Ni layer, annealing is performed to cause a reaction between the Ni layer and polysilicon, thereby forming a silicide layer.
- the silicide composition can be controlled by the few temperature, and in the annealing process in the range of 300 ° C to 35 ° C, Ni 2 Si, 350 in the range of 50 ° C to 65 ° C. It is described that N i S i can be formed by annealing and N i S i 2 can be formed by annealing at 65 ° C. or higher.
- This forming method is characterized in that a metal film is deposited in a region where a silicide layer is to be formed, and then a silicide composition having desired characteristics is formed by annealing humidity.
- Non-Patent Document 2 24 May 1 9 9 9 9 p 3 1 3 7.
- Non-Patent Document 3 Ma ter. R es. S oc. S ymp. P roc. 3 2 0, 1 994 p 22 1
- Non-Patent Document 3 by supplying Ni, Co, and Fe to a silicon substrate at a low rate (low supply speed) using MBE or vapor deposition. It is described that Ni Si 2 , Co Si 2 , and Fe Si 2 are formed directly on the substrate.
- a silicide layer having a Si-rich composition can be formed at a lower temperature than the method described in Non-Patent Document 1.
- Patent Document 1 JP-A-10-144625 discloses that titanium is deposited on a silicon substrate by chemical vapor deposition (CVD) using high-frequency plasma. Titanium silicide with C 54 structure (T i S i 2 ) A method of forming a layer is disclosed. The feature of this technology is that, as in Non-Patent Document 2, it is possible to directly form a silicide layer, so that the annealing process can be reduced.
- Patent Document 2 Japanese Patent Laid-Open No. 8-97249 (hereinafter referred to as Patent Document 2) and Japanese Patent Laid-Open No. 7-297136 (hereinafter referred to as Patent Document 3) include a tetra-salt titanium gas and a hydrogen gas on a silicon substrate. introduced, electron cyclotron resonance, helicon wave, by a CVD method using plasma excitation by ECR, a method of forming a titanium silicide (T i S i 2) layer having a C 54 structure is disclosed.
- the feature of this technique is that, as in Patent Document 1, the silicide layer can be directly formed, so that the annealing process can be reduced.
- Patent Document 4 JP 2000-58484 A (hereinafter referred to as Patent Document 4) describes (1) titanium tetrachloride and hydrogen gas, or (2) titanium tetrachloride and silanic gas on a silicon substrate.
- Patent Document 5 Japanese Patent Laid-Open No. 8-283944 (hereinafter referred to as Patent Document 5) uses titanium tetrachloride and silane gas as raw material gas, adds hydrogen fluoride to the raw material gas, and adds titanium fluoride on the silicon substrate by the CVD method.
- a method of forming a doped film (T i S i 2 ) is disclosed.
- Patent Document 6 Japanese Patent Laid-Open No. 2003-328130 (hereinafter referred to as Patent Document 6) Japanese Patent Application Laid-Open No. 2005-93732 (hereinafter referred to as Patent Document 7) and Non-Patent Document 3, a raw material containing Ni, S A method is described in which a nickel silicide film is formed on a silicon substrate by a CVD method using a raw material containing i.
- Non-Patent Document 4 Ni (PF 3 ) 4, by a CVD method using S i 3 H 8 as a raw material gas containing S i to form a nickel silicide film, this time, varying the composition of the nickel silicon rhino de film by the supply amount of S i 3 H 8 It is stated that it is possible.
- Patent Document 8 discloses the deposition of Pt by the CVD method using Pt (PF 3 ) 4 as a metal source gas.
- P t (PF 3 ) 4 The Pt film is formed by supplying the raw material onto a silicon substrate heated to 300 ° C or less, and P t at temperatures higher than 300 ° C and P t It is described that platinum silicide is formed at the same time.
- Ni is deposited by sputtering, and the Ni / Si composition ratio of nickel silicide is controlled by annealing conditions thereafter.
- the manufacturing cost would be increased.
- the metal film for forming the silicide is formed by sputtering, plasma damage to the device may occur and the device characteristics may be impaired.
- an annealing process of 6500 ° C. or higher is required. Therefore, the resistance of the silicide layer provided on the source / drain region during the annealing is increased.
- Ni contained in the gate electrode diffuses into the gate insulating film and degrades the device characteristics.
- the gate electrode of the non-patent document 1 is a mixed phase of N i S i 2 and N i S i, when using the gate electrode having such a mixed phase, there may become a cause of variations in element characteristics .
- the annealing temperature for obtaining the NiSi crystal phase depends on the type and concentration of impurities on the substrate. It is described as changing. Therefore, the method for forming a silicide layer according to this document has a problem that the annealing temperature needs to be optimized in accordance with the type and concentration of impurities on the substrate, and the number of processes is increased.
- Non-Patent Document 2 and Non-Patent Document 3 It is difficult to form a uniform silicide layer over a large area by a method of forming a silicide layer having a Si-rich composition by supplying a metal at a low rate using a vapor deposition method or a vapor deposition method.
- these documents do not mention anything about the method of changing the silicide composition over a wide range, such as source region, drain region, gate electrode for N-type MOSFET and gate electrode for P-type MOSFET. It was not suitable for forming a silicide layer having an optimum composition corresponding to each part constituting the semiconductor device.
- the source / drain regions, other than the gate electrode region, for example, such as the gate sidewall was also formed on the insulating film, and it was difficult to selectively remove the silicide layer on the gate sidewall in the subsequent etching process.
- Patent Document 5 the formation of a silicide film by CVD using a source gas containing metal and a source gas containing Si in Patent Document 5, Patent Document 6, Patent Document 7, and Non-Patent Document 4 is Drain region, regions other than the gout electrode, for example, on insulating films such as gate sidewalls Also, a silicide layer is formed. Therefore, it is difficult to selectively remove the silicide layer on the gate sidewall in the subsequent etching process.
- the conventional manufacturing method is suitable for forming a silicide layer having an optimum composition corresponding to each of the source / drain region, the gate electrode for the N-type MOSFET and the gate electrode for the P-type MOSFET. There wasn't.
- an object of the present invention is to solve the above-mentioned problems of the prior art.
- a metal compound layer is formed directly on a substrate without adding a process such as annealing, and the yarn of the metal compound layer is formed. It is another object of the present invention to provide a method and a forming apparatus capable of controlling a crystal phase and a manufacturing method of a semiconductor device.
- the present invention has the following configuration.
- a source gas containing a metal capable of forming a metal compound with a semiconductor material is supplied, the substrate is heated to a temperature at which the source gas can be thermally decomposed, and the metal layer is not deposited on the substrate.
- a method of manufacturing a semiconductor device comprising: a step of forming a metal compound layer; and a step of forming a gate electrode using the gate pattern as a gate electrode.
- a container, a substrate holding table provided so as to be able to hold a substrate in the container, a first heater capable of heating the humidity of the substrate holding joint, and a raw material A source gas supply unit that is connected to the container via a gas inlet and is capable of supplying source gas, a second heater that can heat the temperature of the source gas inlet, and the pressure in the container can be adjusted
- a control unit for controlling the pressure in the container, and a metal compound layer forming apparatus comprising: Brief description of the drawings:
- FIG. 1 is a view showing an example of the forming apparatus of the present invention.
- FIG. 2A is a diagram showing a reaction process on the substrate surface in the present invention.
- FIG. 2B shows the reaction process on the substrate surface in the present invention.
- FIG. 2C shows the reaction process on the substrate surface in the prior art.
- FIG. 2D shows the reaction process on the substrate surface in the prior art.
- FIG. 3A shows the raw material decomposition process during silicidation in the prior art.
- FIG. 3B is a diagram showing a raw material decomposition process during silicidation in the present invention.
- Fig. 4A shows the formation of a silicide layer on the trench structure in the prior art.
- Fig. 4B shows the formation of a silicide layer on the trench structure in the prior art.
- FIG. 4C is a view showing a formation state of a silicide layer on the trench structure in the present invention.
- FIG. 4D is a view showing a formation state of a silicide layer on the trench structure in the present invention.
- FIG. 5 is a diagram showing an example of the relationship between the crystal structure of the silicide layer, the raw material supply amount and the substrate temperature in the present invention.
- FIG. 6 is a diagram showing an example of the relationship between the crystal structure of the silicide layer, the raw material supply amount, and the pressure in the vacuum vessel in the present invention.
- FIG. 7 is a diagram showing an example of the relationship between the crystal structure of the silicide layer, the substrate temperature, and the pressure in the vacuum vessel in the present invention.
- FIG. 8A shows the conditions for forming the first and second silicide layers.
- FIG. 8B shows the first and second silicide layers formed under the formation conditions of FIG. 8A.
- FIG. 9A shows the conditions for forming the first and second silicide layers.
- FIG. 9B is a view showing the first and second silicide layers formed under the formation conditions of 9A.
- FIG. 1A shows the conditions for forming the first and second silicide layers.
- FIG. 108 is a diagram showing the first and second silicide layers formed according to the formation conditions of FIG.
- FIG. 11A is a view showing a cross-sectional photograph of the silicide layer in SEM in Example 1 and Comparative Example 1 of the present invention.
- FIG. 11B is a view showing a cross-sectional photograph of the silicide layer in Comparative Example 1 by SEM.
- FIG. 12 is a diagram showing an X RD spectrum of the silicide layer in Example 3 of the present invention.
- Figure 13 shows the XRD spectrum of the silicide layer in Example 4 of the present invention.
- FIG. 14 is a diagram showing a silicide rate when non-doping and impurity doping are performed in Example 5 of the present invention.
- FIG. 15 is a diagram showing the first and second formation conditions in Example 6 of the present invention.
- FIG. 16 is a diagram showing the first and second formation conditions in Example 8 of the present invention.
- FIG. 17 is a diagram showing the first and second formation conditions in Example 10 of the present invention.
- FIG. 18A is a view showing a cross-sectional photograph by SEM of the silicide layer in Example 14 and Comparative Example 2 of the present invention.
- FIG. 18B is a view showing a cross-sectional photograph of the silicide layer in Comparative Example 2 by SEM.
- FIG. 19A shows a cross-sectional structure of the silicide layer manufactured in Reference Example 3 by SEM.
- Figure 19B shows the composition analysis result by XPS of the silicide layer manufactured in Reference Example 3. Best Mode for Carrying Out the Invention:
- the present invention relates to a method for forming a metal compound layer (a silicon metal compound layer, a germanium metal compound layer, or a silicon germanium metal compound layer), a device for forming a metal compound layer, and a method for manufacturing a semiconductor device.
- a metal compound layer for example, a silicide layer provided on the source / drain region required for the quotient performance of MOSFET, a gate electrode, and the like can be cited.
- a source gas containing at least one kind of metal that can form a metal compound layer is exposed, and silicon, germanium, or silicon germanium is exposed, and the source gas can be thermally decomposed. Supplied on a substrate heated to temperature. At this time, the substrate gas exposed only by the thermal decomposition reaction can be selected by setting the source gas supply rate below the supply rate (supply rate) at which metal deposition starts on the substrate. Thus, silicidation can be performed.
- the supply amount of the source gas is set so as to satisfy the following relationship.
- the silicide layer is controlled by controlling the formation conditions (the supply amount of the source gas, the temperature of the substrate, the pressure in the vacuum vessel, etc.).
- the silicide layer formation temperature can be set low.
- FIG. 1 An example of a film forming apparatus used in the embodiment of the present invention is shown in FIG.
- a source gas containing a metal capable of forming a metal compound layer is adjusted to a predetermined flow rate from a source gas source 1 0 1 via a mass flow controller 1 0 2, and a valve 1 0 3, a gas inlet 1 0 8, shower head 1 1
- the yarn is fed into the vacuum vessel (container) 1 1 1 through 0.
- the carrier gas is adjusted to a predetermined flow rate from the carrier gas source 10 4 through the mass flow controller 1 0 5, and is vacuumed through the valve 1 0 6, the gas inlet 1 0 8, and the shower head 1 1 0.
- This source gas may be supplied alone or together with the carrier gas into the vacuum vessel 11 1 1. Further, the carrier gas may be used as a replacement gas when the source gas is not supplied into the vacuum vessel 11 1 1.
- the carrier gas an inert gas that does not react with the source gas is preferably used, and it is preferable that at least one gas selected from the group consisting of N 2 , Ar, and He is included.
- the carrier gas source 10 4, the mass flow controller 1 0 5, and the vano rev 1 0 6 are constant temperature baths that are temperature control devices so as not to affect the temperature of the raw material gas when joining the raw material gas.
- 1 0 7 is controlled to the same temperature as the metal source gas Yes.
- the temperature of the thermostat 10 07 is preferably controlled to be 0 ° C. or higher and 150 ° C. or lower.
- Raw material inlet 1 0 8, shower head 1 1 0 and vacuum vessel 1 1 1, heater 1 0 9, raw material gas 1 0 1 has sufficient vapor pressure by heater 1 1 9 and temperature control device heater 1 1 2
- the temperature is controlled to be higher than the temperature and lower than the decomposition temperature of the raw material gas. Preferably, this temperature is not lower than 0 ° C and not higher than 1550 ° C.
- a substrate 1 1 3 is provided in the vacuum vessel 1 1 1, and a predetermined temperature (source gas is generated on the substrate surface) by a heater 1 1 6 as a heating device through a susceptor 1 1 4 as a substrate support. Is heated to a temperature capable of thermal decomposition). In addition, the susceptor 1 1 4 prevents the raw material gas from entering the heater 1 1 6.
- the source gas supplied to the vacuum vessel 1 1 1 1 ⁇ the source gas and carrier gas that have not been consumed to form the metal compound layer are exhausted through the conductance valve 1 1 8 by the exhaust pump 1 2 ⁇ . .
- the pressure in the vacuum vessel 1 1 1 is controlled by the opening of the conductance valve 1 1 8.
- Reference numeral 1 1 9 is a trap.
- the constant temperature bath 10 7, the mass flow controller 10 0 2 and 1 0 5, the heaters 1 0 9, 1 1 2 and 1 1 6, and the conductance valve 1 1 8 are It is connected to a control unit (not shown), and controlled by the control unit so that no metal layer is deposited on the substrate.
- the conditions under which metal layer deposition does not occur are input to the control unit in advance as the characteristic values of the respective parts, and when the characteristic values of the respective parts deviate from those previously input during operation of the apparatus.
- the control unit issues an instruction so that the characteristic values input in advance to each unit are obtained.
- the characteristic value of each part is maintained at a predetermined value by this control part command.
- the characteristic values of each part can be changed several times during operation of the device.
- the control unit instructs each part to change the formation condition during the formation of the metal compound layer. put out. And changing the formation conditions of the metal compound layer during operation As a result, a plurality of metal compound layers having different compositions and characteristics can be formed.
- FIGS. 2A to 2D show that the metal element is Ni, and using the forming apparatus shown in FIG. 1, a raw material gas containing Ni is supplied onto the silicon substrate to form a silicon metal compound layer ( This shows the case where a silicide layer is formed.
- FIGS. 2A and 2B show the formation mechanism of the silicide layer of the present invention
- FIGS. 2C and 2D show the formation mechanism of the conventional silicide layer.
- the source gas is decomposed by thermal excitation from the substrate in the gas phase or on the substrate surface, and Ni atoms are adsorbed on the substrate surface.
- Ni atoms are adsorbed on the substrate surface.
- adsorption and desorption occur constantly on the substrate surface, and as a whole, a predetermined amount of Ni atoms are adsorbed on the substrate surface as this equilibrium state.
- the amount of Ni adsorbed on the substrate surface is affected by the supply amount of the source gas, the substrate temperature, and the pressure in the vacuum vessel, and can be controlled by these conditions.
- the molecular motion of Ni atoms becomes active, the number of Ni atoms desorbed from the substrate surface increases, and the amount of Ni atoms adsorbed on the substrate in an equilibrium state decreases.
- the pressure in the vacuum chamber is increased, the speed of molecular movement of Ni atoms increases, so the number of Ni atoms desorbed from the substrate surface increases, and the amount of Ni atoms adsorbed on the substrate in an equilibrium state decreases.
- the amount of source gas supplied is increased, the number of Ni atoms supplied to the substrate surface increases, so that a large amount of Ni atoms are easily adsorbed on the substrate surface in an equilibrium state.
- Ni adsorbed on the substrate reacts with silicon and diffuses to form a silicide layer.
- the composition and crystal structure of the silicide layer are determined by the amount of Ni previously adsorbed on the substrate surface in the process of FIG. 2A. For example, when the adsorption amount of Ni is small, Ni Si 2 having a Si rich composition is formed. Furthermore, in accordance with the amount of adsorption of N i increases, N i S i that having a composition of N i Ritsuchi, silicide layer having a crystal phase of N i 3 S i is formed. Therefore, as the conditions for forming the silicide layer, for example, the substrate temperature is lowered and the supply amount of the source gas is increased. If the pressure in the vacuum vessel is lowered, a silicide layer having a Ni-rich composition can be formed.
- Figs. 2C and 2D show the conventional silicide layer formation mechanism in which Ni adsorbed on the substrate surface is larger than the amount consumed by silicidation.
- the substrate is set to a temperature above which the metal can decompose and Ni is supplied, at a very early stage, a predetermined amount of Ni atoms are adsorbed on the surface of the substrate, and these Ni atoms react with Si constituting the substrate. Begin to form silicides.
- an excessive amount of Ni is supplied on the substrate surface one after another in this manner to form the silicide layer, unreacted metal is generated and deposited on the substrate. As a result, a metal Ni layer is formed.
- Ni is not deposited Ni atoms that have been thermally decomposed and adsorbed on the substrate surface, but becomes a deposited metal Ni layer. The phase reaction becomes dominant.
- the method for forming a silicide layer according to the present invention it is important to set the conditions such that the supply amount of the raw material gas is set to be equal to or less than the supply amount at which metal deposition starts on the exposed region. .
- the silicide layer By forming a silicide layer under such conditions, it becomes possible to control the composition and crystal phase of the silicide layer according to the raw material supply conditions.
- the source gas is decomposed in the gas phase by plasma excitation.
- the adsorbed C 1 acts as an impurity on the surface of the substrate and inhibits the adsorption of Ti, which causes a problem that it becomes difficult to inhibit the silicidation reaction and change the composition of the silicide layer.
- C 1 decomposed in the gas phase Is supplied as chlorine radicals on the substrate surface and etches the silicon substrate. In this way, when using the plasma CVD method, silicidation is inhibited and the substrate is damaged due to the influence of the elements contained in the raw material, so a non-uniform silicide layer is formed as shown in the figure.
- FIG. 3B shows an example in which Ni i (PF 3 ) 4 is used as a raw material gas in the raw material decomposition process in the present invention.
- the silicide layer is formed by the reaction between Ni and silicon generated by thermal decomposition of the source gas on the substrate surface. That is, since only Ni of the Ni (PF 3 ) 4 gas is separated on the substrate surface, only Ni can be adsorbed on the substrate surface. As a result, since impurities that inhibit silicidation are not adsorbed on the substrate surface, the formation of the silicide layer can be changed depending on the supply amount of the source gas, and a uniform silicide layer can be formed. it can.
- FIGS. 4A and 4B are compound diagrams in the case where a silicide layer is formed on a silicon substrate having a three-dimensional structure as shown in the figure by using the sputtering method which is a conventional technique.
- the sputtering method which is a conventional technique.
- metal atoms scattered from the target by the plasma reach the substrate with directivity in the direction of the arrow in the figure. Therefore, as shown in the figure, metal atoms cannot be adsorbed on the side walls of the three-dimensional structure, and a silicide layer as shown in Fig. 4B is formed.
- FIGS. 4C and 4D show the case where the silicide layer forming method of the present invention is used.
- the source gas does not have energy associated with plasma excitation as compared with the prior art, and is supplied to the substrate surface in a low-directivity state.
- the metal adsorption state is as shown in Fig. 4C
- a silicide layer with excellent coverage is formed as shown in Fig. 4D by the surface thermal decomposition reaction.
- a silicide layer can be formed by a method having excellent coverage without causing damage to the substrate due to radicals generated by plasma damage.
- the atmospheric temperature in the container holding the substrate is set to a temperature at which the source gas is not thermally decomposed.
- the substrate is set to a temperature that is higher than the ambient temperature in the container and at which the source gas can be thermally decomposed. Therefore, the raw material gas is not thermally decomposed when introduced into the container, but is thermally decomposed on the substrate surface.
- the “temperature at which the raw material gas can be thermally decomposed” is a value specific to the raw material gas and is uniquely determined.
- FIG. 5 is a schematic diagram showing the relationship between the composition of the silicide layer, the supply amount of Ni material, and the substrate temperature when the pressure in the vacuum vessel is constant. For example, if the substrate temperature in FIG. 5 is 300 ° C., the crystal phase of the silicide layer is changed to N i S i 2 , N i S i in sequence as the supply amount of Ni raw material increases. , A silicide layer having a composition and crystal phase of Ni 3 Si and Ni rich (composition on a line parallel to the vertical axis in FIG. 5). The reason why the silicide composition moves to the Ni rich side as the Ni raw material supply amount increases is that the amount of Ni adsorbed on the substrate surface per unit time increases.
- N i 3 S i the composition of shea Risaido, N i S i, ⁇ the composition of the N i S i 2 and S i Ritsuchi
- a silicide layer having a crystalline phase can be formed (composition on a line parallel to the horizontal axis in FIG. 5).
- the silicide composition moves to the Si rich side as the substrate temperature increases.
- the molecular motion of Ni atoms adsorbed on the substrate surface becomes active, and Ni atoms are explained from the substrate surface. To make it easier to wear.
- the substrate temperature is from 200 ° C. to 300 ° C.
- a Ni metal deposition layer is formed on the substrate surface, and the thickness and composition of the silicide layer are increased.
- the Ni metal layer is deposited on the substrate surface in this way because the amount of Ni atoms adsorbed on the substrate surface is larger than the amount of Ni atoms adsorbed on the substrate and consumed for forming the silicide layer. Accumulated.
- the substrate temperature should be not less than the temperature at which the source gas is thermally decomposed and not more than the temperature at which the amount of metal element adsorbed and desorbed on the exposed substrate surface is equal. Specifically, it is preferably in the range of 150 ° C or more and 600 ° C or less.
- Figure 6 shows the relationship between the composition of the silicide layer, the supply amount of Ni material, and the pressure in the vacuum vessel when the substrate temperature is kept constant. From Fig. 6, when the substrate degree and the supply amount of Ni raw material are constant, increasing the pressure in the vacuum vessel results in the following sequence: Ni 3 Si, Ni Si i, Ni Si 2 Si-rich composition ⁇ Silicide layer with crystalline phase can be formed (composition on a line parallel to the horizontal axis in Fig. 6). This is because the movement speed of Ni atoms on the substrate surface increases as the pressure in the vacuum vessel increases, making it less likely to be adsorbed on the substrate surface.
- the pressure in the vacuum chamber is preferably 1.33 X 10 4 Pa (100 Torr) or less, and moreover, the source gas is not decomposed in the gas phase without being decomposed. In order to cause a decomposition reaction by thermal excitation and form a silicide layer, 1. 33 X 10 3 Pa (l OT orr) or less is more preferable.
- FIG. 7 shows the relationship between the formation of the silicide layer, the substrate temperature, and the pressure in the vacuum vessel when the Ni supply amount is constant. From Fig. 7, when the Ni source gas supply rate is constant, the pressure inside the vacuum vessel is kept constant and the substrate temperature is increased (composition on a straight line parallel to the vertical axis in Fig. 7). , As above Each has a rich Si composition. Further, in FIG. 7, when the substrate humidity and the substrate temperature is constant, increasing the pressure in the vacuum chamber, in turn, N i 3 S i, N i S i, N i S i 2 and S i Ritsuchi This makes it possible to form a silicide layer having a crystal phase (composition on a line parallel to the vertical axis in FIG. 7).
- the experiments shown in FIGS. 5 to 7 were carried out using a standard compound diameter 6-inch substrate and a metal compound layer forming apparatus.
- the formation time of the metal compound layer was 2 O m i n.
- the substrate temperature by optimizing the pressure and the raw material gas supply amount in the vacuum chamber, the crystal of N i S i 2, N i S i, N i 3 S i A silicide layer having a phase can be formed. This is because the Ni absorption amount on the substrate surface is related to the substrate temperature, the pressure in the vacuum container, and the amount of material gas supplied.
- the substrate is made of silicon and the silicide layer is formed as the metal compound layer has been described.
- the relationship between the substrate temperature, the pressure in the vacuum vessel, the supply amount of the source gas, and the composition of the crystal phase is that the substrate is made of germanium or silicon germanium, and the germanium metal compound layer, The same holds true when forming a silicon germanium compound layer.
- a plurality of metal compound layers having different compositions and properties can be formed by changing the formation conditions of the metal compound layer.
- the first metal compound layer is formed under the first formation conditions (first formation step), and when the first metal compound layer reaches a predetermined film thickness,
- the metal compound layer may be formed by forming the second metal compound layer on the first metal compound layer under the formation condition 2 (second formation step).
- the second formation condition is less than the first formation condition, and at least a source gas (a metal capable of forming a metal compound layer such as a silicon metal compound layer, a germanium metal compound layer, or a silicon Kermanium metal compound layer).
- a source gas a metal capable of forming a metal compound layer such as a silicon metal compound layer, a germanium metal compound layer, or a silicon Kermanium metal compound layer.
- the amount of metal element contained in the metal compound layer with respect to the film thickness direction as shown in Fig. 8B. Can be changed.
- the second metal compound layer is formed on the first metal compound layer under the formation conditions (second formation step).
- the second formation condition is at least lower in substrate temperature than the first formation condition.
- the first metal compound layer is formed under the first formation condition (first formation step), and when the first metal compound layer reaches a predetermined film thickness, the first metal compound layer is formed under the second formation condition.
- a second metal compound layer is formed on the metal compound layer (second forming step). At this time, the second forming condition increases the metal content in the source gas compared to the first forming condition.
- the amount of the metal element contained in the second metal compound layer formed under the second formation condition from the viewpoint of process resistance and resistance to the etching process or the like is the same as that in the first metal compound layer formed under the first formation condition. It is preferable that the amount is larger than the amount of the metal element contained in.
- the raw material supply amount, the substrate temperature, and the pressure in the vacuum container under the first and second formation conditions are as shown in FIGS. Select the optimum conditions from the conditions shown in Fig. 7 and execute each be able to.
- the formation methods (1) to (4) described above can be used not only when forming a silicide layer as a metal compound layer but also when forming a germanium metal compound layer and a silicon germanium compound layer. it can.
- the metal compound layers having different compositions and crystal phases are not limited to two layers as described above, and three or more layers may be provided.
- the metal compound layer is composed of a plurality of layers, the metal elements contained in the metal compound constituting each layer may be the same.
- the metal element contained in the source gas is preferably at least one metal selected from the group consisting of Ni, Pt, Co, W and Ru from the viewpoint of resistance value and work function. Further, when C is contained in the element constituting the source gas, C is adsorbed on the substrate surface, and silicidation reaction is suppressed. Accordingly, it is preferable that C is not included in the elements constituting the source gas.
- the source gases are Ni (PF 3 ) 4 , Ni (BF 2 ) 4 , P t (PF 3 ) 4 , P t (BF 2 ) 4 , Co (PF 3 ) 6 , Co (BF 2 ) It is preferably at least one raw material selected from the group consisting of 6 , W (PF 3 ) 6 , W (BF 2 ) 6 , Ru (PF 3 ) 5 and Ru (BF 2 ) 5 .
- the relationship between the formation conditions of the silicon metal compound layer (silicide layer) (substrate temperature, pressure in the vacuum vessel, supply amount of the source gas) and the silicide composition to be formed when the above various source gases are used Indicates.
- N i (PF 3) 4 or N i (BF 2) 4 when the raw material gas is N i (PF 3) 4 or N i (BF 2) 4, N i S i 2, A silicide layer having a crystal phase of N i S i or N i 3 S i can be formed.
- the substrate temperature is preferably 150 ° C. or higher and 600 ° C. or lower in order to form a silicide layer having. Also, in the region where the substrate temperature is less than 250 ° C, the thermal decomposition reaction of the source gas on the substrate surface is suppressed, so that the silicide layer formation rate decreases. Also, the substrate temperature should be 400 ° C In the region exceeding the above, desorption of metal from the substrate occurs, so that the formation rate of the silicide layer becomes slow. Therefore, the substrate temperature is more preferably 250 ° C or more and 400 ° C or less.
- the pressure in the vacuum vessel is preferably 1.33 X 10 4 Pa (l O OTorr) or less in order to suppress vapor phase decomposition components of the source gas, and the source gas splitting angle and source material only on the substrate surface 1.
- 33X 10— 2 Pa (1 X 10— 4 Torr) or more, 1. 33 X 10 3 Pa ( 1 OTorr) The following is more preferable.
- a Ni Si 2 crystal phase can be formed at a temperature of 300 ° C. or lower, which is lower than that of the prior art, and is suitable for reducing the silicide formation temperature. It is shown that
- the substrate temperature is preferably 250 ° C or higher and 600 ° C or lower.
- the substrate temperature is more preferably 250 ° C or higher and 400 ° C or lower.
- the pressure in the vacuum vessel is preferably 1.06 X 10 4 Pa (80 Torr) or less in order to suppress the gas phase decomposition component of the source gas, and the source gas is decomposed only on the substrate surface.
- crystal phase of the silicide layer by the supply amount of, 1. 33 X 10- 2 P a (1 X 10 - 4 T orr) over 1. 33 X 10 3 P a ( 10 Torr) I prefer the following ⁇ ⁇ .
- the substrate temperature is preferably 250 ° C. or higher and 500 ° C. or lower. Also, in the region where the substrate humidity exceeds 400 ° C, metal deposition from the substrate occurs, resulting in a slow formation rate of the silicide layer. Accordingly, the substrate temperature is more preferably 250 ° C or higher and 400 ° C or lower.
- the pressure in the vacuum vessel is preferably 1. 33 X 10 3 Pa (l OTo rr) or less in order to suppress gas phase decomposition components of the source gas, and only on the substrate surface.
- a first silicide layer having a Ni Si 2 crystal phase is formed under the first formation condition (first 1 A silicidation step), and a second silicide layer having at least one of the Ni Si and Ni 3 Si crystal phases can be formed under the second formation condition (second silicidation step).
- the second silicide layer having an N i S i crystalline phase to the first silicide layer it is preferable to form the second silicide layer having an N i S i crystalline phase to the first silicide layer to have a N i S i 2 crystal phase.
- the optimum material conditions are selected from the conditions shown in FIGS. 5, 6, and 7 for the raw material supply amount, the substrate temperature, and the pressure in the vacuum container in the first and second forming conditions. Can be implemented respectively.
- the raw material gas is C o (PF 3) 6 or Co (BF 2) 6
- the raw material gas is C o (PF 3) e or the C o (BF 2) 6, C o S i 2
- C A silicide layer having a crystal phase of either o Si or Co 3 Si can be formed.
- the substrate temperature is 0.99 ° C or higher It is preferably 600 ° C or lower, and preferably 250 ° C or higher and 400 ° C or lower to ensure the formation rate.
- the pressure in the vacuum vessel is preferably 1.33X 10 4 Pa (l O OT orr) or less. To secure the formation rate, 13.3 Pa (0. l To rr) or more 1. 33 X 10 3 Pa (10 Torr) or less is more preferable.
- the substrate humidity is 250 ° C or higher to form a silicide layer with a composition of Co Si and crystal phase It is preferably 600 ° C or lower, and more preferably 250 ° C or higher and 400 ° C or lower to ensure the formation rate.
- the pressure in the vacuum vessel is preferably 1.33 X 10 4 Pa (l O OTo rr) or less. From the viewpoint of controllability of the formation rate, 1. 33 X 10- 2 Pa (IX 10— 4 To rr ) Above 1. 33 X l 0 3 Pa (l OTo rr) or less is more preferable.
- the substrate temperature is 250 ° C to form a silicide layer with the composition and crystal phase of Co 3 Si. More than 500 ° C. is preferable, and in order to secure the formation rate, 250 to 400 is more preferable.
- the pressure in the vacuum vessel is preferably 1. 33 X l 0 4 Pa (l O OTo rr) or less, and from the viewpoint of controllability of the formation rate, 1. 33 X 10— 2 P a (1 X 10— 4 T orr), 1.33 X 10 3 Pa (10 Torr) or less is more preferable.
- a first silicide layer having a Co Si 2 crystal phase is formed under the first formation conditions (first silicidation).
- a second silicide layer having a Co 3 Si crystal phase can be formed under a second formation condition (second silicidation step).
- the raw material gas is C o (PF 3) 6 or Co (BF 2) 6, from the viewpoint of process resistance and resistance against the etching, has a crystal phase of C o S i on C o S i 2 It is more preferable to form a silicide layer.
- a silicon substrate or a silicon oxide film formed with a film thickness of 10 to 20 nm using a CVD method on a silicon substrate is used, and a film thickness of 50 to 150 nm is formed on this substrate by a CVD method. What formed the polysilicon layer was used.
- the polysilicon layer non-doped, As-doped, and B-doped substrates were used according to the examples or comparative examples.
- the silicide layer is formed on the substrate using the forming apparatus shown in Fig. 1.
- the substrate temperature is 150 ° C to 700 ° C and the pressure in the vacuum chamber is 1.
- the temperatures of the vacuum vessel, gas supply system, gas inlet, and shower head were set to 150 ° C or less (the temperature at which the source gas was not thermally decomposed).
- N 2 was used as a carrier gas.
- the supply amount of the source gas is set in the range of 2 sccm to 100 sccm by the mass flow controller according to the examples or comparative examples. It was supplied onto the substrate in the range of lm in to l O O min in.
- the conditions were set such that the Ni layer was deposited on the substrate or not.
- a silicide layer was formed under the condition that no Ni metal stack was formed on the substrate surface.
- the pressure in the vacuum chamber during the formation of this silicide layer is 3.33 X 10 2 Pa (2.5 Torr)
- source gas supply time is 45 min
- source gas supply rate is 20 sccm
- substrate temperature was set to 360 ° C.
- Ni (PF 3 ) 4 was used as the source gas.
- 360. C corresponds to a temperature at which Ni i (PF 3 ) 4 that is a raw material gas can be thermally decomposed.
- Fig. 11A shows the cross-sectional structure of this silicide layer.
- the polysilicon layer can be uniformly silicided without the formation of a Ni metal deposition layer on the substrate surface. From TEM evaluation, it was confirmed that there was no Ni deposited layer on the surface and no damage caused by etching caused by the source gas.
- a silicide layer was formed under the condition that a Ni metal deposition layer was formed on a substrate having a non-doped polysilicon layer.
- the substrate temperature during the formation of this silicide layer is 296 ° C
- the pressure inside the vacuum vessel is 3.33 X 10 2 Pa (2.5 Torr)
- the supply time of the source gas is 2 Omin
- the supply amount of the source gas was set to 80 sccm.
- Ni (PF 3 ) 4 was used as the source gas. Note that 296 ° C corresponds to a temperature at which Ni i (PF 3 ) 4 that is a raw material gas can be thermally decomposed.
- Figure 11 B shows the cross-sectional structure of this silicide layer.
- a Ni metal layer is deposited on the substrate, only a very thin silicide layer is formed on the surface area of the polysilicon, and the entire polysilicon layer is silicided. It can be seen that it is difficult to make it.
- This silicide layer is in a state where the Ni metal layer is not yet deposited on the polysilicon layer at the start of the supply of the source gas. It is thought that Ni in the source gas was formed by reaction with polysilicon. (Example 2)
- a non-doped polysilicon layer with a thickness of 150 nm is used as the substrate, the substrate temperature is 296 ° C, the pressure in the vacuum vessel is 3.33 X 10 2 Pa (2.5 Torr), and the feed time of the source gas is 2 Om Set to in, and the supply amount of the source gas was changed. Ni (PF 3 ) 4 was used as the source gas. With each source gas supply rate, the silicide layer could be formed uniformly without depositing Ni on the substrate surface.
- Figure 12 shows the dependence of the raw material gas supply rate on the XRD spectrum of the crystalline phase of the silicide layer thus formed.
- the crystal phase of the silicide layer by increasing only the supply amount of the raw material gas, in turn, N i S i 2, N i S i, yarn N i 3 S i and N i Ritsuchi ⁇ It can be seen that a silicide layer having a crystalline phase can be formed. In addition, it can be seen that there is no spectrum due to the mixed phase of each crystal phase at each raw material gas supply amount, and it has good crystallinity.
- the crystalline phase of the silicide layer can be changed without performing annealing treatment corresponding to the crystal structure that has been conventionally required. It can be formed with good controllability. Further, it was confirmed that the uniform N i S i 2 crystal phase is formed also in the following substrate temperature 300 ° C.
- a vacuum container using a substrate with a 150 nm thick non-doped polysilicon layer The substrate pressure was changed to 3.33 X 10 2 Pa (2.5 Torr), the source gas supply rate was set to 20 sccm, and the source gas supply time was set to 30 min to 60 min to change the substrate temperature.
- Ni (PF 3 ) 4 was used as the source gas.
- a uniform silicide layer could be formed without Ni deposition on the substrate surface.
- Fig. 13 shows the dependence of the substrate temperature of the XRD spectrum on the crystal phase of the silicide layer formed in this way 1 ". Note that 264 ° C is the source gas Ni (PF 3 )
- the crystal phase of the silicide layer by the increasing only the substrate temperature connexion, in order, N i 3 S i, N i S i, N i S i 2 and the composition of the S i Ritsuchi. Crystal It can be seen that a silicide layer having a phase can be formed.
- the crystal phase of the silicide layer can be formed with good controllability without performing annealing treatment corresponding to the crystal structure that has been required in the past. be able to.
- the silicide layer was formed in order by increasing the pressure in the vacuum vessel without changing the substrate humidity and the raw material supply amount, so that N i 3 S i, N i S i, N i S i It was confirmed that a silicide layer having a crystal phase with a composition of 2 and S i -rich could be formed.
- a silicide layer having a crystal phase with a composition of 2 and S i -rich could be formed.
- the region exceeding 1.33 X 10 4 Pa (l O OT orr) decomposition of the source gas in the gas phase is promoted, and the composition and crystal phase are controlled by the thickness of the silicide layer and the formation conditions. Confirmed that it would be difficult.
- the decomposition of the source gas in the gas phase is suppressed, and the control range of the composition and crystal phase depends on the formation rate and formation conditions of the silicide layer. It was confirmed that securing was compatible.
- the raw material supply amount, the substrate temperature, the pressure in the vacuum vessel and the composition of the silicide layer to be formed are summarized as follows: Fig. 5, Fig. 6, Fig. 7 Become.
- the filled in circles, black triangles, black squares show the silicide layer having N i S i 2 formed respectively by using the present embodiment, N i S i, the composition-crystal phase of N i 3 S i .
- the black diamond in the figure shows a Ni metal layer deposited on the substrate surface. This shows a situation where it is difficult to change the film thickness, composition, and crystal phase composition of the silicide layer depending on the formation conditions.
- X in the figure indicates that the decomposition of the source gas in the gas phase is promoted, making it difficult to change the thickness, composition, and crystal phase of the silicide layer depending on the formation conditions.
- the supply amount of the source gas is set to be equal to or less than the supply amount at which the deposition of Ni starts, so that the supply amount of the source gas, the substrate temperature, and the pressure in the vacuum vessel This indicates that the composition of the silicide layer and the crystal phase can be formed over a wide range with good controllability.
- a 80 nm thick polysilicon layer was undoped and 6 ⁇ 10 15 cm 2 was doped by ion implantation of As and B, respectively, as impurities.
- the silicide layer was formed under the conditions of a substrate temperature of 300 ° C, a pressure in the vacuum vessel of 3.33 X 10 2 Pa (2.5 Torr), a raw material supply amount of 2 sccm, and a formation time of 85 min.
- Ni (PF 3 ) 4 was used as the source gas. Note that 30 O ° C corresponds to a temperature at which Ni i (PF 3 ) 4 that is a raw material gas can be thermally decomposed.
- the silicide layer could be formed uniformly without Ni deposition on the substrate surface.
- Figure 14 shows the silicide layer formation rate in these cases.
- the silicide rate is specified by the non-doped silicide rate (the formation speed of the silicide layer in the thickness direction).
- the method for forming a silicide layer according to the present invention does not significantly change the formation rate and crystal phase regardless of the amount of impurities and the type of impurities in the silicide layer formation region at low temperatures, and the impurities are doped. It is shown to be suitable for forming a silicide layer on a fabricated substrate. (Example 6)
- the first formation conditions are as follows: substrate temperature 300 ° C, pressure in vacuum vessel 3. 33X 10 2 Pa (2.5 Torr), source gas is introduced at 2 sccm for 80 min to form the first silicide layer (first silicidation), and then the substrate temperature is 300 ° C under the second formation condition, vacuum vessel The inside pressure was 3.33 X 10 2 Pa (2.5 Torr), and the source gas was introduced at 20 sccm for 200 sec to form a second silicide layer (second silicidation). Ni (PF 3 ) 4 was used as the source gas.
- the substrate temperature is 300 ° C and the pressure in the vacuum vessel is 3.33 X 10 2 Pa (2.5 Torr), 8 Omin in source gas at 2 sccm, is introduced to form the first silicide layer (first silicidation).
- 300 ° C pressure in the vacuum vessel 3.33 X 10 2 Pa (2.5 Torr)
- source gas was introduced at 50 sccm for 200 sec to form a second silicide layer (second silicidation) ).
- Ni (PF 3 ) 4 was used as the source gas.
- the silicide layer could be uniformly formed without Ni deposition on the substrate surface.
- the substrate humidity is 360 ° C and the pressure in the vacuum vessel is 3.33 under the first forming conditions.
- X 10 2 Pa (2.5 Torr) source gas is introduced at 20 sccm for 45 min to form the first silicide layer (first silicidation).
- Ni (PF 3 ) 4 was used as the source gas.
- the silicide layer could be uniformly formed without depositing Ni on the substrate surface.
- the substrate temperature was 360 ° C under the first formation conditions, and the pressure in the vacuum vessel was 3.33 X 10 2 P a (2.5 Torr), Source gas is introduced at 20 sccm for 45 min to form the first silicide layer (first silicidation), and then the substrate temperature is 360 ° C under the second formation condition.
- the pressure inside the vacuum vessel was 1.33 Pa (0. OlTorr) and the source gas was introduced at 20 sccm for 10 min to form a second silicide layer (second silicidation).
- Ni (PF 3 ) 4 was used as the source gas.
- the substrate temperature under the first formation condition is 360 ° C, and the pressure in the vacuum chamber is 3.33 X 10 2 P a (2.5 Torr)
- Source gas is introduced at 45 sc at 20 sccm to form the first silicide layer (first silicidation)
- the substrate condition is adjusted under the second formation condition.
- 300 ° C the pressure in the vacuum vessel is 3.33 X 10 2 Pa (2.5 To rr)
- a source gas was introduced at 20 sccm at 1 Omin to form a second silicide layer (second silicidation).
- Ni (PF 3 ) 4 was used as the source gas.
- the silicide layer could be formed uniformly without Ni deposition on the substrate surface.
- the substrate temperature in the first formation condition is 450 ° C and the pressure in the vacuum chamber is 3.33 X 10 2 P a (2.5 Torr), source gas at 80 scc ni for 30 min, introduction to form a first silicide layer (first silicidation), and then substrate temperature at 300 ° C under the second formation condition, Set the pressure inside the vacuum vessel to 3.33 X 10 2 Pa ( 2.5 T
- a source gas was introduced at 80 sccm for 5 min to form a second silicide layer (second silicidation).
- Ni (PF 3 ) 4 was used as the source gas.
- a uniform silicide layer could be formed without depositing Ni on the substrate surface.
- 450 ° C. corresponds to a temperature at which Ni i (PF 3 ) 4 that is a raw material gas can be thermally decomposed.
- the silicide layer formation profile allows the formation of a silicide layer with continuously different composition and crystal phase, indicating that the number of steps can be reduced compared to the conventional technology. Yes.
- a silicide layer was formed on a silicon substrate having a trench-structured non-doped polysilicon layer.
- the formation conditions at this time were: 20 sccm of raw material supply, vacuum container The internal pressure was set to 3.33 X 10 3 Pa (25 Torr), the substrate temperature was set to 300 ° C, and the raw material supply time was set to 20 min. Ni (PF 3 ) 4 was used as the source gas.
- the silicide layer could be uniformly formed on the substrate surface without accumulating Ni. It was also confirmed that the silicide layer could be formed uniformly without accumulating Ni metal along the side of the trench structure.
- a silicon substrate, a substrate having a 35 nm thick silicon oxide film, and a non-doped polysilicon layer having a thickness of 80 nm were used, and a silicide layer was formed from this polysilicon layer.
- the silicidation conditions were set as follows: source gas supply rate 2 sccm, source supply time 85 min, substrate temperature 300 ° C, vacuum vessel pressure 3.33 X 10 2 Pa (2.5 Torr) . Ni (PF 3 ) 4 was used as the source gas. At this time, it was possible to form a uniform silicide layer without depositing Ni on the substrate surface. When this silicide layer was used as a gate electrode and evaluation of the cake characteristics was made, no deterioration of the work characteristics due to silicidation was observed.
- Example 13 an example using a silicon substrate was shown. However, even when a germanium substrate or a silicon germanium substrate is used, the supply amount of the source gas is less than the supply amount at which Ni deposition starts. By setting to, Ni could be contained without depositing Ni on the surface of the germanium substrate or silicon germanium substrate. It was also confirmed that the Ni content can be varied depending on the amount of source gas supplied, the substrate temperature, and the pressure in the vacuum chamber. It was also confirmed that by optimizing the formation profile, a layered structure can be formed in germanium or silicon germanium in which the Ni content increases or increases at the top.
- the silicide layer was formed by setting the temperature of the inlet 108 of the forming apparatus shown in FIG. 1 to 160 ° C.
- a substrate having a non-doped polysilicon layer is used, the substrate temperature is 296 ° C, and the source gas is Ni (PF 3 ). 4 was supplied under the conditions of 20 sccm and 2 Omin.
- the pressure in the vacuum chamber was set at 3. 3 3 X 1 0 2 P a (2. 5 T orr).
- Figure 18A shows the SEM cross-sectional observation results of the silicide layer formed in this embodiment. From Fig. 18A, it can be seen that when the temperature of the gas inlet is 160 ° C, the silicide layer is hardly formed. This suggests that the source gas is decomposed at the gas inlet and does not reach the substrate to be processed.
- a silicide layer was formed in the same manner as in Reference Example 3 except that the temperature of the gas inlet 10 8 was set to 1550 ° C. At this time, it was possible to form a uniform silicide layer on the substrate surface without accumulating Ni. This silicide layer is shown in Fig. 18B. Unlike FIG. 18A above, it can be seen that a silicide layer is formed. Therefore, it is necessary to control the temperature at the inlet to below 150 ° C.
- Example 2 the same conditions as in Example 1 were set, except that a silicide layer was formed using Pt (PF 3 ) 4 as a source gas. Note that 360 ° C. corresponds to a temperature at which P t (PF 3 ) 4 that is a raw material gas can be thermally decomposed. In this example, the same evaluation as in Example 1 was performed. As a result, formation of a silicide layer was confirmed under conditions where no Pt metal layer was deposited on silicon.
- the first silicide layer is formed under the first formation condition (first silicidation), and the second silicide layer is continuously formed under the second formation condition in which the amount of material supply is larger than the first formation condition.
- second silicidation it was confirmed that a second silicide layer having a high Pt content could be formed on the first silicide layer formed under the first formation conditions.
- the substrate temperature at the time of the first and second silicidation is 300 ° C.
- the pressure in the vacuum vessel is the same as 3.3 3 X 10 2 Pa (2.5 Torr)
- the supply time of the source gas during the first and second silicidation was 45 min and l Omin, respectively.
- the first silicide layer was formed under the first formation condition (first silicidation), and the second silicide layer was continuously formed under the second formation condition where the substrate humidity was lower than the first formation condition.
- second silicidation the first silicidation formed under the first formation conditions. It was confirmed that a second silicide layer having a high Pt content can be formed on the upper part of the gate layer.
- the pressure in the vacuum vessel during the first and second silicidation is 3.33 X 10 2 Pa (2.5 Torr), and the supply amount of the source gas is the same as 20 sccm. 2
- the source gas supply time for silicidation was 45 min and l Omin, respectively.
- the first silicide layer is formed under the first formation condition (first silicidation), and the second silicide is continuously formed under the second formation condition where the pressure in the vacuum vessel is lower than that in the first formation condition.
- second silicidation it was confirmed that a second silicide layer with a high Pt content could be formed on top of the first silicide layer formed under the first formation conditions.
- the substrate temperature during the first and second silicidation is 300 ° C
- the supply amount of the source gas is the same as 20 sccm
- the supply time of the source gas during the first and second silicidation is set respectively. 45 min, l O min in.
- Example 2 the same conditions as in Example 1 were set, except that a silicide layer was formed using Co (PF 3 ) 6 as a source gas. 360 ° C is the source gas C
- PF 3 0 (PF 3 ) 6 corresponds to the humidity at which pyrolysis is possible.
- a silicide layer could be formed under the condition that no Co metal layer was deposited on silicon.
- Example 16 the raw material supply amount, when changing the pressure of the substrate temperature and the vacuum vessel, C o S i 2 by the change in these conditions, C o S i, Ito ⁇ configuration of C o S i 3 ⁇ It was confirmed that a silicide layer having a crystalline phase could be formed.
- Co S the formation profile of the silicide layer as in Example 1, Co S
- a silicide layer having a CoSi compositional crystal phase can be formed on 1 2 .
- a silicide layer having a laminated structure in which the metal content of the silicide layer increases in the upper part can be formed by optimizing the formation profile of the silicide layer in the same manner as in Example 1.
- FIGS. 19A and 19B show the SEM cross-sectional observation results and the XPS composition analysis results of the silicide layers formed in this embodiment.
- the substrate to be processed was a silicon substrate.
- the formation of the silicide layer proceeds only locally, and the metal Pt layer is formed on the substrate. From the composition analysis by XPS, it can be seen that the metal Pt layer contains a lot of C. This indicates that C constituting the source gas is adsorbed on the substrate surface and inhibits silicidation. Therefore, it can be seen that it is preferable that C is not included as a constituent element of the source gas.
- a metal film is deposited on a region where a metal compound layer is to be formed (such as on a polysilicon region), and then an annealing process is performed. It is possible to form a metal compound layer in a single step without going through such a process. For this reason, the number of processes can be reduced.
- the formation temperature of the silicide layer having the Si-rich composition / crystal phase is lowered. For this reason, it is possible to prevent an excessive load from being applied to the component parts of the device such as the silicide layers on the source / drain regions.
- the composition, crystal phase and formation rate of the metal compound layer are based on A metal compound layer having a desired composition can be formed without being affected by the type and concentration of impurities on the plate.
- a uniform metal compound layer with a large area can be formed without damaging the element during the raw material decomposition process or damaging the substrate due to the raw material gas.
- a three-dimensional structure with good coverage and wraparound characteristics is suitable for forming a metal compound layer in a trench structure with a high aspect ratio.
- the metal compound layer forming apparatus of the present invention since decomposition of the raw material in the raw material supply system can be suppressed, the controllability of the formation of the metal compound layer and the maintainability of the apparatus can be improved.
- the metal compound layer forming method and semiconductor device manufacturing method and apparatus of the present invention are applied to the manufacture of electrode barrier layers, cap layers and the like of semiconductor devices.
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US12/227,714 US7968463B2 (en) | 2006-05-25 | 2007-05-21 | Formation method of metallic compound layer, manufacturing method of semiconductor device, and formation apparatus for metallic compound layer |
JP2008517919A JP5280843B2 (ja) | 2006-05-25 | 2007-05-21 | 金属化合物層の形成方法、及び金属化合物層の形成装置 |
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Cited By (6)
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US7723176B2 (en) | 2005-09-01 | 2010-05-25 | Nec Corporation | Method for manufacturing semiconductor device |
WO2011099467A1 (ja) * | 2010-02-12 | 2011-08-18 | Jsr株式会社 | ルテニウム膜形成用材料及びルテニウム膜形成方法 |
JP2012507865A (ja) * | 2008-11-05 | 2012-03-29 | マイクロン テクノロジー, インク. | 複数のトランジスタゲートの形成方法、および少なくとも二つの異なる仕事関数を有する複数のトランジスタゲートの形成方法 |
US8692320B2 (en) | 2006-05-11 | 2014-04-08 | Micron Technology, Inc. | Recessed memory cell access devices and gate electrodes |
JP2016072352A (ja) * | 2014-09-29 | 2016-05-09 | 株式会社東芝 | 半導体装置の製造方法 |
US9543433B2 (en) | 2006-05-11 | 2017-01-10 | Micron Technology, Inc. | Dual work function recessed access device and methods of forming |
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US8860174B2 (en) | 2006-05-11 | 2014-10-14 | Micron Technology, Inc. | Recessed antifuse structures and methods of making the same |
US20130277816A1 (en) | 2012-04-18 | 2013-10-24 | Texas Instruments Incorporated | Plastic-packaged semiconductor device having wires with polymerized insulator skin |
JP5770806B2 (ja) * | 2013-10-02 | 2015-08-26 | 田中貴金属工業株式会社 | 化学蒸着法によるSi基板上へのニッケル薄膜、及び、Si基板上へのNiシリサイド薄膜の製造方法 |
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US7723176B2 (en) | 2005-09-01 | 2010-05-25 | Nec Corporation | Method for manufacturing semiconductor device |
US8692320B2 (en) | 2006-05-11 | 2014-04-08 | Micron Technology, Inc. | Recessed memory cell access devices and gate electrodes |
US9502516B2 (en) | 2006-05-11 | 2016-11-22 | Micron Technology, Inc. | Recessed access devices and gate electrodes |
US9543433B2 (en) | 2006-05-11 | 2017-01-10 | Micron Technology, Inc. | Dual work function recessed access device and methods of forming |
JP2012507865A (ja) * | 2008-11-05 | 2012-03-29 | マイクロン テクノロジー, インク. | 複数のトランジスタゲートの形成方法、および少なくとも二つの異なる仕事関数を有する複数のトランジスタゲートの形成方法 |
WO2011099467A1 (ja) * | 2010-02-12 | 2011-08-18 | Jsr株式会社 | ルテニウム膜形成用材料及びルテニウム膜形成方法 |
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JP2016072352A (ja) * | 2014-09-29 | 2016-05-09 | 株式会社東芝 | 半導体装置の製造方法 |
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US20090170252A1 (en) | 2009-07-02 |
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KR20090009938A (ko) | 2009-01-23 |
JP5280843B2 (ja) | 2013-09-04 |
US7968463B2 (en) | 2011-06-28 |
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