TW201026876A - Nickel-containing film-formation material, and nickel-containing film-fabrication method - Google Patents
Nickel-containing film-formation material, and nickel-containing film-fabrication method Download PDFInfo
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- TW201026876A TW201026876A TW98131624A TW98131624A TW201026876A TW 201026876 A TW201026876 A TW 201026876A TW 98131624 A TW98131624 A TW 98131624A TW 98131624 A TW98131624 A TW 98131624A TW 201026876 A TW201026876 A TW 201026876A
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- Prior art keywords
- nickel
- containing film
- film
- forming
- film according
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Links
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 401
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 160
- 239000000463 material Substances 0.000 title claims abstract description 71
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- 238000000034 method Methods 0.000 title description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 22
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 19
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 16
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 15
- NZIHMSYSZRFUQJ-UHFFFAOYSA-N 6-chloro-1h-benzimidazole-2-carboxylic acid Chemical compound C1=C(Cl)C=C2NC(C(=O)O)=NC2=C1 NZIHMSYSZRFUQJ-UHFFFAOYSA-N 0.000 claims description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims description 11
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 9
- -1 anthracene compound Chemical class 0.000 claims description 9
- 229910052707 ruthenium Inorganic materials 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 7
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Natural products C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 claims description 6
- DIOQZVSQGTUSAI-UHFFFAOYSA-N n-butylhexane Natural products CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 5
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- QDKSGHXRHXVMPF-UHFFFAOYSA-N 2,2-dimethylundecane Chemical compound CCCCCCCCCC(C)(C)C QDKSGHXRHXVMPF-UHFFFAOYSA-N 0.000 claims description 3
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 3
- GTJOHISYCKPIMT-UHFFFAOYSA-N 2-methylundecane Chemical compound CCCCCCCCCC(C)C GTJOHISYCKPIMT-UHFFFAOYSA-N 0.000 claims description 2
- KUZXQXCWRNFIHK-UHFFFAOYSA-N 3,3-diethyldodecane Chemical compound CCCCCCCCCC(CC)(CC)CC KUZXQXCWRNFIHK-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 150000003304 ruthenium compounds Chemical class 0.000 claims description 2
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 claims description 2
- DIOQZVSQGTUSAI-NJFSPNSNSA-N decane Chemical compound CCCCCCCCC[14CH3] DIOQZVSQGTUSAI-NJFSPNSNSA-N 0.000 claims 1
- 230000007935 neutral effect Effects 0.000 claims 1
- 238000005229 chemical vapour deposition Methods 0.000 abstract description 42
- 230000015572 biosynthetic process Effects 0.000 abstract description 40
- 206010010144 Completed suicide Diseases 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 18
- 238000002441 X-ray diffraction Methods 0.000 description 15
- 238000004458 analytical method Methods 0.000 description 13
- 238000003786 synthesis reaction Methods 0.000 description 13
- 239000000758 substrate Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000004868 gas analysis Methods 0.000 description 8
- 238000006303 photolysis reaction Methods 0.000 description 8
- 208000037998 chronic venous disease Diseases 0.000 description 7
- 238000000151 deposition Methods 0.000 description 7
- 230000008021 deposition Effects 0.000 description 7
- 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 5
- 238000011156 evaluation Methods 0.000 description 5
- WKFBZNUBXWCCHG-UHFFFAOYSA-N phosphorus trifluoride Chemical compound FP(F)F WKFBZNUBXWCCHG-UHFFFAOYSA-N 0.000 description 5
- 230000015843 photosynthesis, light reaction Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000010884 ion-beam technique Methods 0.000 description 4
- 239000003446 ligand Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 150000002815 nickel Chemical class 0.000 description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 238000005979 thermal decomposition reaction Methods 0.000 description 3
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 2
- RPDFRSKJKOQCIT-UHFFFAOYSA-N 3-ethyldodecane Chemical compound CCCCCCCCCC(CC)CC RPDFRSKJKOQCIT-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 2
- AMJMBJIZKKMZIE-UHFFFAOYSA-N difluoro(methyl)phosphane Chemical compound CP(F)F AMJMBJIZKKMZIE-UHFFFAOYSA-N 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 238000001182 laser chemical vapour deposition Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- FEBJSGQWYJIENF-UHFFFAOYSA-N nickel niobium Chemical compound [Ni].[Nb] FEBJSGQWYJIENF-UHFFFAOYSA-N 0.000 description 2
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 238000002230 thermal chemical vapour deposition Methods 0.000 description 2
- GKEUODMJRFDLJY-UHFFFAOYSA-N 1-Methylfluorene Chemical compound C12=CC=CC=C2CC2=C1C=CC=C2C GKEUODMJRFDLJY-UHFFFAOYSA-N 0.000 description 1
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000012327 Ruthenium complex Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 150000001785 cerium compounds Chemical class 0.000 description 1
- LAXIOTUSRGRRNA-UHFFFAOYSA-N cyclopenta-1,3-diene nickel Chemical compound [Ni].C1C=CC=C1.C1C=CC=C1 LAXIOTUSRGRRNA-UHFFFAOYSA-N 0.000 description 1
- DOYIBAKSKZZYPC-UHFFFAOYSA-N cyclopenta-1,3-diene;nickel(2+);prop-1-ene Chemical compound [Ni+2].[CH2-]C=C.C=1C=C[CH-]C=1 DOYIBAKSKZZYPC-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- IAOQICOCWPKKMH-UHFFFAOYSA-N dithieno[3,2-a:3',2'-d]thiophene Chemical compound C1=CSC2=C1C(C=CS1)=C1S2 IAOQICOCWPKKMH-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 150000002816 nickel compounds Chemical class 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- CXXKWLMXEDWEJW-UHFFFAOYSA-N tellanylidenecobalt Chemical compound [Te]=[Co] CXXKWLMXEDWEJW-UHFFFAOYSA-N 0.000 description 1
- XSOKHXFFCGXDJZ-UHFFFAOYSA-N telluride(2-) Chemical compound [Te-2] XSOKHXFFCGXDJZ-UHFFFAOYSA-N 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/04—Nickel compounds
- C07F15/045—Nickel compounds without a metal-carbon linkage
-
- 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
- C23C16/06—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
- C23C16/18—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 from metallo-organic compounds
-
- 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
- C23C16/42—Silicides
-
- 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
-
- 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
- H01L21/28556—Deposition of conductive or insulating materials for electrodes conducting electric current from a gas or vapour, e.g. condensation of conductive layers on semiconductor bodies comprising elements of Group IV of the Periodic Table by chemical means, e.g. CVD, LPCVD, PECVD, laser CVD
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Chemical Vapour Deposition (AREA)
- Electrodes Of Semiconductors (AREA)
Abstract
Description
201026876 六、發明說明： 【發明所屬之技術領域】 本發明係關於含鎳膜之形成材料及含鎳膜之製造方法 。更詳細而言，係關於藉CVD(化學氣相成長法）形成膜所 用之含鎳膜之形成材料及使用該材料之含鎳膜之製造方法 Φ 【先前技術】 目前，半導體裝置中之技術進步極爲顯著，爲了使更 高速之動作成爲可能，因此快速的進行高度化及細微化， 爲此而積極進行材料之開發。 電路材料中不斷導入低阻抗材料、且藉由在閘極電極 、源極電極或汲極之擴散層上形成矽化物膜，而進行更低 的阻抗化。至於此處使用之矽化物膜，已檢討導入比矽化 鈦膜或矽化鈷膜更低阻抗之矽化鎳膜。 此矽化鎳膜之形成以往係藉由濺鑛法進行。然而，濺 鍍法有物理性損傷半導體元件之疑慮，且由於難以均一成 膜，故近幾年來，已探討藉化學氣相成長法（以下亦稱爲 「CVD」）形成膜。 CVD係將膜形成材料揮發爲氣體狀態流動，於反應器 內利用化學反應，於矽基板上堆積膜之方法。CVD藉由在 減壓下成膜，而可在低溫進行成膜，但隨著所用之膜形成 材料之不同，成膜時之條件亦大爲不同。作爲對此時所用 之膜形成材料所要求之特性舉例有具有高蒸氣壓等。 -5- 201026876 迄今所提案之含鎳膜之形成材料中，具有高蒸氣壓之 化合物，經報導有雙（烷基環戊二烯基）鎳（例如參考專利文 獻1)、環戊二烯基烯丙基鎳（例如參考專利文獻2)、肆（三 氟膦）鎳（例如參考專利文獻3)。 然而，雙（烷基環戊二烯基）鎳或環戊二烯基烯丙基鎳 由於作爲配位子之環戊二烯基之碳與鎳相互作用強，故有 所形成之含鎳膜中容易殘存碳之問題。若殘存碳，則有例 如含鎳膜之阻抗値增加之傾向。 β201026876 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a material for forming a nickel-containing film and a method for producing a nickel-containing film. More specifically, it relates to a material for forming a nickel-containing film used for forming a film by CVD (Chemical Vapor Growth) and a method for producing a nickel-containing film using the same. [Prior Art] At present, technological progress in a semiconductor device It is extremely remarkable, and in order to make higher-speed movements possible, it is rapidly becoming more advanced and miniaturized, and actively develops materials for this purpose. A low-impedance material is continuously introduced into the circuit material, and a vaporization film is formed on the diffusion layer of the gate electrode, the source electrode, or the drain electrode to perform lower impedance. As for the vaporized film used herein, it has been reviewed to introduce a reduced nickel film which is lower in impedance than a titanium telluride film or a cobalt telluride film. The formation of this nickel-deposited nickel film has conventionally been carried out by a sputtering method. However, the sputtering method has a problem of physically damaging a semiconductor element, and since it is difficult to form a film uniformly, it has been considered in recent years to form a film by a chemical vapor growth method (hereinafter also referred to as "CVD"). CVD is a method in which a film forming material is volatilized into a gaseous state, and a film is deposited on a tantalum substrate by a chemical reaction in a reactor. CVD can be formed at a low temperature by forming a film under reduced pressure, but the conditions at the time of film formation vary greatly depending on the film forming material used. The characteristics required for the film forming material used in this case are exemplified by high vapor pressure and the like. -5-201026876 A compound having a high vapor pressure among the materials for forming a nickel-containing film proposed so far, has been reported to have bis(alkylcyclopentadienyl)nickel (for example, refer to Patent Document 1), cyclopentadienyl group. Allyl nickel (for example, refer to Patent Document 2) and iridium (trifluorophosphine) nickel (for example, refer to Patent Document 3). However, bis(alkylcyclopentadienyl)nickel or cyclopentadienylallyl nickel has a strong interaction with nickel due to the cyclopentadienyl group as a ligand, so a nickel-containing film is formed. It is easy to survive the problem of carbon. If carbon remains, there is a tendency that the impedance 値 of the nickel-containing film increases, for example. β
又，肆（三氟膦）鎳由於作爲配位子之三氟膦之磷之非 共用電子對與鎳之相互作用弱，故所形成之含鎳膜中不易 殘存碳，但有成膜時因配位子之P-F鍵斷裂而副生成HF 之問題。若副生成HF，則有所形成之含鎳膜損傷之傾向 〇 因此，期望開發出一種藉由CVD形成之含鎳膜中不 易殘存碳且不易副生成HF之材料。 先前技術文獻 ® 專利文獻 專利文獻1 :特開20 03-328130號公報 專利文獻2:特開2005-93732號公報 專利文獻3 :特開2006-45649號公報 【發明內容】 [發明欲解決之課題] 本發明爲解決如上述之過去技術所伴隨之問題者’本 -6 - 201026876 發明提供一種含鎳膜之形成材料，其在所形成之含鎳膜上 不易殘存碳且不易副生成HF。另外，本發明係提供含鎳 膜之形成材料，其中含鎳膜爲鎳膜或矽化鎳膜。 另外’本發明之另一目的係提供一種使用上述含鎳膜 之形成材料之含鎳膜之製造方法。另外，本發明係提供含 錬膜之製造方法’其中含鎳膜爲鎳膜或矽化鎳膜。 Φ [解決課題之手段] 本發明者等針對上述課題進行檢討之結果，發現若使 用含有至少一種以特定構造表示之鎳錯合物之含鎳膜之形 成材料’則可藉由CVD形成穩定之膜，且形成之含鎳膜 中不易殘存碳’且成膜時不易副生成HF。再者，發現上 述含鎳膜之形成材料適於形成矽化鎳膜。本發明之含鎳膜 之形成材料尙未有任何報導。 亦即，本發明係關於下列。 W [】] —種含鎳膜之形成材料，其特徵爲包含選自由Further, ruthenium (trifluorophosphine) nickel has a weak interaction with nickel due to the unshared electron pair of phosphorus as a ligand of trifluorophosphine, so that carbon is less likely to remain in the formed nickel-containing film, but there is a film formation factor. The PF bond of the ligand is broken to generate HF. When HF is formed by-product, there is a tendency for the formed nickel-containing film to be damaged. Therefore, it has been desired to develop a material which does not easily retain carbon in the nickel-containing film formed by CVD and which is less likely to generate HF by-product. PRIOR ART DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT The present invention has been made in order to solve the problems associated with the prior art as described above. The present invention provides a material for forming a nickel-containing film which is less likely to retain carbon on the formed nickel-containing film and which is less prone to HF formation. Further, the present invention provides a forming material of a nickel-containing film in which a nickel-containing film is a nickel film or a nickel telluride film. Further, another object of the present invention is to provide a method for producing a nickel-containing film using the above-described nickel-containing film forming material. Further, the present invention provides a method for producing a ruthenium-containing film, wherein the nickel-containing film is a nickel film or a nickel telluride film. Φ [Means for Solving the Problem] As a result of reviewing the above problems, the present inventors have found that the formation of a nickel-containing film containing at least one nickel complex represented by a specific structure can be stabilized by CVD. In the film, and in the formed nickel-containing film, carbon is not easily retained, and HF is not easily formed in the film formation. Further, it has been found that the above-mentioned nickel-containing film forming material is suitable for forming a nickel telluride film. The material for forming a nickel-containing film of the present invention has not been reported. That is, the present invention relates to the following. W []] - a nickel-containing film forming material characterized by comprising
Ni(PF2(CF3))4、Ni(PF(CF3)2)4、Ni(P(CF3)3)4、Ni(PF2R2)4 、Ni(PFR3R4)4 及 NUPFaNI^R5：^ 所組成群組（其中，rLr5 各獨立表示Η、碳數ι~6之烷基或苯基）之至少一種鎳錯 合物。 [2] 如[1]所述之含鎳膜之形成材料，其中前述鎳錯合 物爲 Ni(PF2(CF3))4。 [3] 如[1]所述之含鎳膜之形成材料，其中前述鎳錯合 物爲 N i (P F (C F 3) 2) 4。 201026876 [4] 如π]所述之含鎳膜之形成材料，其中前述鎳錯合 物爲 Ni(p(CF3)3)4。 [5] 如Π]所述之含鎳之膜形成材料，其中前述鎳錯合 物爲NUP^R2)4(其中’ R2表示H、碳數^6之烷基或苯 基）。 [6] 如[5]所述之曰鎳膜之形成材料，其中前述 爲-CH3、-C2H5、-C3H7 或-C 4 Η 9。 [7] 如[1]所述之含鎳膜之形成材料，其中前述鎳錯合 物爲NUPFW)4(其中’ R3及R4各獨立表示Η、碳數丨〜6 之烷基或苯基）。 [8] 如[7]所述之含鎳膜之形成材料，其中前述以及R4 各獨立爲-CH3、-C2H5、-(：3117或-(：4只9。 [9] 如[1]所述之含錬膜之形成材料，其中前述鎳錯合 物爲Ni(PF2NRiR5)4(其中’以及R5各獨立表示η、碳= 1〜6之烷基或苯基）。 [10] 如[9]所述之含鎳膜之形成材料，其中前述Rl及 〇 R5 各獨立爲-H、-CH3、-C2H5、-(^3{^7或_(^41{9。 [U]如Π]〜no]中任一項所述之含鎳膜之形成材料， 其係用於藉由CVD(化學氣相成長法）之膜形成中。 [12] 如[l]~[u]中任一項所述之含鎳膜之形成材料， 其中含鎳膜爲鎳膜或矽化鎳膜。Groups of Ni(PF2(CF3))4, Ni(PF(CF3)2)4, Ni(P(CF3)3)4, Ni(PF2R2)4, Ni(PFR3R4)4, and NUPFANI^R5:^ (wherein rLr5 each independently represents at least one nickel complex of hydrazine, an alkyl group having 1 to 6 carbon atoms or a phenyl group). [2] The material for forming a nickel-containing film according to [1], wherein the nickel complex is Ni(PF2(CF3))4. [3] The material for forming a nickel-containing film according to [1], wherein the nickel complex is N i (P F (C F 3) 2) 4 . 201026876 [4] The material for forming a nickel-containing film according to π], wherein the nickel complex is Ni(p(CF3)3)4. [5] The nickel-containing film forming material according to the above, wherein the nickel complex is NUP^R2)4 (wherein 'R2 represents H, an alkyl group having 6 carbon atoms or a phenyl group). [6] The material for forming a niobium nickel film according to [5], wherein the aforementioned is -CH3, -C2H5, -C3H7 or -C4?9. [7] The nickel-containing film forming material according to [1], wherein the nickel complex is NUPFW) 4 (wherein 'R3 and R4 each independently represent an anthracene, an alkyl group having a carbon number of 66 or a phenyl group) . [8] The material for forming a nickel-containing film according to [7], wherein the foregoing and R4 are each independently -CH3, -C2H5, -(:3117 or -(:4 only 9. [9] as [1] The material for forming a ruthenium-containing film, wherein the nickel complex is Ni(PF2NRiR5)4 (wherein 'and R5 each independently represent η, carbon = 1 to 6 alkyl or phenyl). [10] as [9] The material for forming a nickel-containing film, wherein each of R1 and R5 is independently -H, -CH3, -C2H5, -(^3{^7 or _(^41{9. [U]如Π] The material for forming a nickel-containing film according to any one of the above-mentioned items, which is used for film formation by CVD (Chemical Vapor Growth). [12] As in any of [l] to [u] The material for forming a nickel-containing film according to the invention, wherein the nickel-containing film is a nickel film or a nickel telluride film.
[13] 如[I2]所述之含鎳膜之形成材料，其中前述砂化 鎳膜之Si源係以SiaH2a + 2(其中’ a爲之整數）或RbSiH 其中，b爲1~3之整數，R表示碳數丨〜3之烷基）之構造式 -8 - 201026876 所表示之至少一種矽化合物。 [I4]如[13]所述之a錬膜之形成材料，其中前述砂化 合物爲矽烷、二矽烷、三矽烷、甲基矽棱、二甲基砂院、 三甲基矽烷、乙基矽烷、二乙基矽烷或3乙基砂院。 [15] —種含錬膜之製造方法’其特徵爲使用如 [1]〜[14]中任一項所述之含鎳膜之形成材料，藉由CVD(化 學氣相成長法）形成含鎳膜。 ❹ [發明之效果] 依據本發明’可藉由CVD形成穩定之含鎮膜，形成 之含鎳膜中不易殘存碳且膜形成時不易副生成HF。亦即 ，使用本發明之含鎳膜之形成材料，藉由CVD可輕易地 形成良好之含鎳膜，進而可輕易地形成良好之砂化鎳膜。 【實施方式】 以下就本發明之含鎳膜之形成材料加以詳細說明。 本發明之含鎳膜之形成材料其特徵爲包含選自由 Ni(PF2(CF3))4、Ni(PF(CF3)2)4、Ni(P(CF3)3)4、Ni(PF2R2)4 、Ni(PFR3R4)4 及 成群組（其中，R1 〜R5 各獨立表示H、碳數1〜6之烷基或苯基）之至少一種鎳錯 合物。 上述鎳錯合物較好爲 Ni(PF2(CF3))4、Ni(PF(CF3)2)4、 Ni(P(CF3)3)4、Ni(PF2R2)4(其中，R2 表示 Η、碳數 1 〜6 之 烷基或苯基）、NiiPFzNRiR5)^其中，R1及R5各獨立表示 201026876 Η、碳數1〜6之烷基或苯基），更好爲Ni(PF2(CF3))4、 Ni(PF(CF3)2)4、Ni(PF2R2)4(其中，R2 表示 η、碳數 1~6 之 烷基或苯基）。若爲該等鎳錯合物，則有蒸氣壓變高之傾 向。又，該等鎳錯合物由於揮發性高，因此可適用於使膜 形成材料揮發而進行成膜之方法，例如CVD。 本發明之含鎳膜之形成材料包含例如Ni(PF2R2)4(其中 ，R2表示H、碳數1〜6之烷基或苯基）。[13] The material for forming a nickel-containing film according to [I2], wherein the Si source of the foregoing nickel carbide film is SiaH2a + 2 (wherein 'a is an integer) or RbSiH, wherein b is an integer of 1 to 3 , R represents at least one anthracene compound represented by Structural Formula -8 - 201026876 of carbon number 丨 〜3 alkyl. [I4] The material for forming a film according to [13], wherein the sand compound is decane, dioxane, trioxane, methyl fluorene, dimethyl sand, trimethyl decane, ethyl decane, Diethyl decane or 3 ethyl sand yard. [15] A method for producing a ruthenium-containing film, which is characterized in that the material for forming a nickel-containing film according to any one of [1] to [14] is formed by CVD (Chemical Vapor Growth) Nickel film. [Effects of the Invention] According to the present invention, a stable film-containing film can be formed by CVD, and carbon is less likely to remain in the formed nickel-containing film, and HF is less likely to be formed when the film is formed. Namely, by using the nickel-containing film forming material of the present invention, a good nickel-containing film can be easily formed by CVD, and a good nickel-formed film can be easily formed. [Embodiment] Hereinafter, a material for forming a nickel-containing film of the present invention will be described in detail. The nickel-containing film forming material of the present invention is characterized by comprising Ni (PF2(CF3)) 4, Ni(PF(CF3)2)4, Ni(P(CF3)3)4, Ni(PF2R2)4, Ni(PFR3R4)4 and at least one nickel complex of the group (wherein R1 to R5 each independently represent H, an alkyl group having 1 to 6 carbon atoms or a phenyl group). The above nickel complex is preferably Ni(PF2(CF3))4, Ni(PF(CF3)2)4, Ni(P(CF3)3)4, Ni(PF2R2)4 (wherein R2 represents ruthenium, carbon) a number of 1 to 6 alkyl or phenyl), NiiPFzNRiR5) wherein R1 and R5 each independently represent 201026876 Η, an alkyl group having 1 to 6 carbon atoms or a phenyl group, more preferably Ni(PF2(CF3))4 Ni(PF(CF3)2)4, Ni(PF2R2)4 (wherein R2 represents η, an alkyl group having 1 to 6 carbon atoms or a phenyl group). In the case of such a nickel complex, there is a tendency that the vapor pressure becomes high. Further, since these nickel complexes have high volatility, they are suitable for a method of forming a film by volatilizing a film forming material, for example, CVD. The material for forming a nickel-containing film of the present invention contains, for example, Ni(PF2R2)4 (wherein R2 represents H, an alkyl group having 1 to 6 carbon atoms or a phenyl group).
Ni(PF2R2)4 中之 R2 較好爲- CH3、-C2H5、-C3H7 或- C4H9 ° Ni(PF2R2)4 之具體例舉例爲 Ni(PF2(CH3))4、Ni(PF2(C2H5))4 、Ni(PF2(C3H7))4 或 Ni(PF2(C4H9))4。若爲該等鎳錯合物 ，則有蒸氣壓變高之傾向。又，該鎳錯合物由於揮發性高 ’因此可適當地使用於使膜之形成材料揮發而進行成膜之 方法，例如CVD。 本發明之含鎳膜之形成材料包含例如Ni(PFR3R4)4(其 中，R3及R4各獨立表示H、碳數1~6之烷基或苯基）。A preferred example of R2 in Ni(PF2R2)4 is -CH3, -C2H5, -C3H7 or -C4H9 ° Ni(PF2R2)4 is Ni(PF2(CH3))4, Ni(PF2(C2H5))4 Ni (PF2(C3H7))4 or Ni(PF2(C4H9))4. In the case of such a nickel complex, the vapor pressure tends to be high. Further, since the nickel complex has a high volatility, it can be suitably used in a method of forming a film by volatilizing a film forming material, for example, CVD. The material for forming a nickel-containing film of the present invention contains, for example, Ni(PFR3R4)4 (wherein R3 and R4 each independently represent H, an alkyl group having 1 to 6 carbon atoms or a phenyl group).
Ni(PFR3R4)4 中之 R3 及 R4 較好各獨立爲- (：Η3、-(：2：Η5 、-C3H7 或-C4H9。Ni(PFR3R4)4 之具體例舉例爲 Ni(PF(CH3)2)4 、Ni(PF(C2H5)2)4、Ni(PF(C3H7)2)4 或 N i (P F (C 4 Η 7) 2) 4。若 爲該等鎳錯合物，則有蒸氣壓變高之傾向。又，該等錬錯 合物由於揮發性高，因此可適當地使用於使膜之形成材半斗 揮發而進行成膜之方法，例如CVD。 本發明之含鎳膜之形成材料包含例如 其中，R1及R5各獨立表示Η、碳數1〜6之烷基或苯基）。 NUPFzNWr5；^中之R1及R5較好各獨立爲-Η' -CH3 201026876 、-C2H5、-C3H7 或-C4H9。NKPFeWR5：^ 之具體例舉例爲R3 and R4 in Ni(PFR3R4)4 are preferably each independently - (: Η3, -(:2: Η5, -C3H7 or -C4H9. Ni(PFR3R4)4 is exemplified by Ni(PF(CH3)2) 4, Ni(PF(C2H5)2)4, Ni(PF(C3H7)2)4 or N i (PF (C 4 Η 7) 2) 4. If it is such a nickel complex, there is vapor pressure Further, since the ruthenium complex has high volatility, it can be suitably used for a method of forming a film by volatilizing a film forming material, for example, CVD. Formation of a nickel-containing film of the present invention The material includes, for example, wherein R1 and R5 each independently represent an anthracene, an alkyl group having 1 to 6 carbon atoms or a phenyl group. NUPFzNWr5; wherein R1 and R5 are each independently -Η' -CH3 201026876, -C2H5, - A specific example of C3H7 or -C4H9. NKPFeWR5:^ is
Ni(PF2NH(CH3))4、Ni(PF2N(CH3)2)4、Ni(PF2NH(C2H5))4、 Ni(PF2N(C2H5)2)4、Ni(PF2NH(C3H7))4、Ni(PF2N(C3H7)2)4 、：Ni(PF2NH(C4H7))4 或 Ni(PF2N(C4H7)2)4。若爲該等鎳錯 合物’則有蒸氣壓變高之傾向。又，該等鎳錯合物由於揮 發性高’因此可適當地使用於使膜之形成材料揮發而進行 成膜之方法，例如CVD。 © 使用包含至少一種如上述之鎳錯合物之含鎳膜之形成 材料時，形成之含鎳膜中不易殘存碳且膜形成時不易副生 成HF。尤其是可藉由CVD輕易地形成含鎳膜。 本發明之含鎳膜之形成材料亦可包含上述之兩種以上 之鎳錯合物。又’本發明之含鎳膜之形成材料亦可包含氦 、氖、氬或氪等稀有氣體。 本發明之含鎳膜形成材料中含有之鎳錯合物之製造方 法可藉由習知之方法製造。例如，可藉由使四羰基鎳或二 環戊二烯鎳等與作爲目的之鎳錯合物之配位子進行配位子 交換而製造。 另外’鎳錯合物亦可依據需要藉由習知之方法純化。 純化之方法舉例爲例如蒸餾或吸附。 本發明之含鎳膜之形成材料較好使用於藉由CVD之 成膜中’但只要是利用含鎳膜之形成材料之蒸汽之成膜方 法即可，而並不限定於CVD。 本發明之含鎳膜之製造方法係使用上述含鎳膜之形成 材料，藉由化學氣相成長法（CVD)成膜。 -11 - 201026876 至於含鎳膜之製造方法可利用使Ni源的上述鎳錯合 物分解之各種CVD。亦即，各種CVD舉例爲以熱分解之 熱CVD'藉由熱及光分解之光CVD、以電漿活性化光分 解之電漿CVD、以雷射活性化光分解之雷射補助CVD、 以離子束活性化光分解之離子束補助CVD等。該等之各 種CVD均可被利用作爲含鎳膜之成膜方法。 形成含鎳膜時之反應壓力較好爲0.0013〜101.3kPa， 更好爲 〇.〇13~101.3kPa，又更好爲0_13〜101.3kPa。另外 ，反應溫度較好爲50〜800 °C，更好爲100-500 °C。 使用本發明之含鎳膜之形成材料所形成之含鎳膜較好 爲鎳膜或矽化鎳膜。 鎳膜或矽化鎳膜必須使用上述鎳錯合物作爲Ni源。 又，矽化鎳膜之Si源較好爲以SiaH2a + 2(其中，a爲1~3之 整數）或RbSiH4_b(其中，b爲1〜3之整數，R表示碳數1〜3 之烷基）之構造式表示之至少一種矽化合物，更好爲矽烷 、二矽烷、三矽烷、甲基矽烷、二甲基矽烷、三甲基矽烷 、乙基矽烷、二乙基矽烷、三乙基矽烷。使用該等矽化合 物作爲矽化鎳膜之Si源時，會有蒸氣壓變高之傾向。 鎳膜或矽化鎳膜之製造方法可利用使爲Ni源之上述 鎳錯合物分解之各種CVD。亦即，各種CVD舉例爲以熱 分解之熱CVD、藉由熱及光分解之光CVD、以電漿活性 化光分解之電漿CVD、以雷射活性化光分解之雷射補助 CVD、以離子束活性化光分解之離子束補助CVD等。該 等之各種CVD均可被利用於鎳膜或矽化鎳膜之成膜。又 201026876 ，於使矽化鎳膜之Si源之上述矽化合物分解時亦可以同 樣方法利用各種CVD。 形成鎳膜或矽化鎳膜時之反應壓力較好爲〇.〇〇 13〜101.3 kPa，更好爲 0.013〜1 01.3kPa，又更好爲 0.13-101.3 kPa ° 又，反應溫度較好爲50~800°C，更好爲1〇〇〜500°C。 使用本發明之含鎳膜之形成材料所製造之含鎳膜若在 還原劑存在下製造，則Ni或Si容易還原。至於還原劑舉 Φ 例爲氫等。 實施例 以下藉由實施例詳細說明本發明，但本發明並不受該 等之限制。 [合成例1] • Ni(PF2(CF3))4 之合成 該錯合物係依據化學學會期刊（AHJournal of the Chemical Society(A))，7, pi 1 3 6( 1 967)中所述之方法合成。 首先，於500毫升之不鏽鋼製耐壓容器中導入12克經昇 華純化之Ni(C5H5)2及48克PF2(CF3)並經密閉後，在60°C下 加熱40小時。加熱後，以蒸餾分餾無色液體。以GC-MS(HP 製造之 HP6890/JEOL 製造之 JMS-AutomassII)、ICP-AES(SII製造之 VISTA-PRO)及有機元素分析裝置（LECO 製造之 CHNS-932)分析所分餾之無色液體後，鑑定爲 Ni(PF2(CF3))4(28 克，產率 75%)。 -13- 201026876 [合成例2] • Ni(PF(CF3)2)4 之合成 該錯合物係依據化學學會期刊（A)(J〇urnal of the Chemical Society(A))，7，pll 36(1 967)中所述之方法合成。 首先，於500毫升之不鏽鋼製耐壓容器中導入5.8克經昇 華純化之Ni(C5H5)2及43克PF(CF3)2並經密閉後，在室溫 下攪拌1小時。隨後，以昇華分餾無色結晶。以GC-MS(HP製 @ 造之 HP6890/JEOL 製造之 JMS-AUTOMASSII)、ICP-AES(SII製造之 VISTA-PRO)及有機元素分析裝置（LECO 製造之CHNS-932)分析所分餾之無色結晶後，鑑定爲 Ni(PF(CF3)2)4(20 克，產率 83%)。 [合成例3]Ni(PF2NH(CH3))4, Ni(PF2N(CH3)2)4, Ni(PF2NH(C2H5))4, Ni(PF2N(C2H5)2)4, Ni(PF2NH(C3H7))4, Ni(PF2N (C3H7) 2) 4 , : Ni(PF2NH(C4H7))4 or Ni(PF2N(C4H7)2)4. In the case of these nickel compounds, the vapor pressure tends to be high. Further, since these nickel complexes have high volatility, they can be suitably used in a method of forming a film by volatilizing a film forming material, for example, CVD. © When a material containing a nickel-containing film containing at least one of the nickel complexes described above is used, carbon is less likely to remain in the formed nickel-containing film and HF is less likely to be formed when the film is formed. In particular, a nickel-containing film can be easily formed by CVD. The material for forming a nickel-containing film of the present invention may further comprise two or more of the above nickel complexes. Further, the material for forming a nickel-containing film of the present invention may contain a rare gas such as helium, neon, argon or xenon. The method for producing a nickel complex contained in the nickel-containing film forming material of the present invention can be produced by a conventional method. For example, it can be produced by ligand-exchange of a nickel tetracarbonyl or a nickel dicyclopentadiene with a ligand of the intended nickel complex. Further, the nickel complex can be purified by a conventional method as needed. The method of purification is exemplified by, for example, distillation or adsorption. The material for forming a nickel-containing film of the present invention is preferably used in the film formation by CVD, but it is not limited to CVD as long as it is a film forming method using a vapor-forming material of a nickel-containing film. The method for producing a nickel-containing film of the present invention is formed by chemical vapor deposition (CVD) using the above-described material for forming a nickel-containing film. -11 - 201026876 As for the method for producing a nickel-containing film, various CVDs which decompose the above-described nickel complex of the Ni source can be used. That is, various CVDs are exemplified by thermal CVD by thermal decomposition CVD by thermal and photolysis, plasma CVD by plasma-activated photolysis, and laser-assisted CVD by laser-activated photolysis. Ion beam-activated photodecomposition ion beam assisted CVD or the like. Each of these CVDs can be utilized as a film forming method of a nickel-containing film. The reaction pressure at which the nickel-containing film is formed is preferably from 0.0013 to 101.3 kPa, more preferably from ~13 to 101.3 kPa, still more preferably from 0_13 to 101.3 kPa. Further, the reaction temperature is preferably from 50 to 800 ° C, more preferably from 100 to 500 ° C. The nickel-containing film formed using the material for forming a nickel-containing film of the present invention is preferably a nickel film or a nickel telluride film. For the nickel film or the nickel telluride film, the above nickel complex must be used as the Ni source. Further, the Si source of the niobium nickel film is preferably SiaH2a + 2 (where a is an integer of 1 to 3) or RbSiH4_b (wherein b is an integer of 1 to 3, and R is an alkyl group having 1 to 3 carbon atoms) The formula represents at least one hydrazine compound, more preferably decane, dioxane, trioxane, methyl decane, dimethyl decane, trimethyl decane, ethyl decane, diethyl decane, triethyl decane. When these ruthenium compounds are used as the Si source of the niobium-deposited nickel film, the vapor pressure tends to be high. As the method for producing the nickel film or the nickel telluride film, various CVDs which decompose the above nickel complex which is a source of Ni can be used. That is, various CVDs are exemplified by thermal CVD by thermal decomposition, photo CVD by thermal and photodecomposition, plasma CVD by plasma-activated photolysis, and laser-assisted CVD by laser-activated photolysis. Ion beam-activated photodecomposition ion beam assisted CVD or the like. These various CVDs can be utilized for film formation of a nickel film or a nickel telluride film. Further, in 201026876, various CVDs can be used in the same manner when the above-mentioned cerium compound of the Si source of the bismuth telluride film is decomposed. The reaction pressure when forming the nickel film or the nickel telluride film is preferably 〇13〇〇101.3 kPa, more preferably 0.013~1 01.3 kPa, still more preferably 0.13-101.3 kPa °, and the reaction temperature is preferably 50~ 800 ° C, preferably 1 〇〇 ~ 500 ° C. When a nickel-containing film produced using the material for forming a nickel-containing film of the present invention is produced in the presence of a reducing agent, Ni or Si is easily reduced. As for the reducing agent, Φ is hydrogen. EXAMPLES Hereinafter, the present invention will be specifically described by examples, but the present invention is not limited thereto. [Synthesis Example 1] • Synthesis of Ni(PF2(CF3))4 This complex is based on the AH Journal of the Chemical Society (A), 7, pi 1 3 6 (1 967). Method synthesis. First, 12 g of sublimated purified Ni(C5H5)2 and 48 g of PF2 (CF3) were introduced into a 500 ml stainless steel pressure vessel and sealed, and then heated at 60 ° C for 40 hours. After heating, the colorless liquid was fractionated by distillation. After analyzing the fractionated colorless liquid by GC-MS (JMS-Automass II manufactured by HP6890/JEOL manufactured by HP), ICP-AES (VISTA-PRO manufactured by SII), and an organic element analyzer (CHNS-932 manufactured by LECO), It was identified as Ni(PF2(CF3))4 (28 g, yield 75%). -13- 201026876 [Synthesis Example 2] • Synthesis of Ni(PF(CF3)2)4 This complex is based on J〇urnal of the Chemical Society (A), 7, pll 36 Synthesized by the method described in (1 967). First, 5.8 g of sublimated purified Ni(C5H5)2 and 43 g of PF(CF3)2 were introduced into a 500 ml stainless steel pressure vessel and sealed, and stirred at room temperature for 1 hour. Subsequently, the colorless crystals were fractionated by sublimation. Analysis of fractionated colorless crystals by GC-MS (JMS-AUTOMASSII manufactured by HP6890/JEOL manufactured by HP), ICP-AES (VISTA-PRO manufactured by SII), and organic element analyzer (CHNS-932 manufactured by LECO) Thereafter, it was identified as Ni(PF(CF3)2)4 (20 g, yield 83%). [Synthesis Example 3]
Ni(PF2(CH3))4 之合成 該錯合物係依據無機化學（Inorganic Chemistry)第4 φ 冊，65 1 (1 96S)中所述之方法合成。首先，於500毫升之不 鏽鋼製耐壓容器中加入6.5克之Ni(CO)4，導入甲基二氟膦 (24克）並經密閉後，使容器在150°C下加熱12小時。加熱後 ，以蒸餾分餾無色液體。以GC-MS(HP製造之HP6890/JEOL 製造之 JMS-AUTOMASSII)、ICP-AES(SII 製造之 VISTA-PRO)及有機元素分析裝置（LECO製造之CHNS-932)分析所 分餾之無色液體後，鑑定爲Ni(PF2(CH3))4(肆（甲基二氟膦 ))鎳）（1 1克，產率7 2 %)。 -14- 201026876 [實施例l] • Ni(PF2(CF3))4之成膜評價 [實施例1-1] 對合成例1中獲得之Ni(PF2(CF3))4，使用示差熱熱重 量同時測定裝置（SII製造之TG/DTA6200)，求得加熱至 5 0 0 °C時之揮發率’爲9 9.8質量％。揮發殘留物極少，可 © 知係適用作含鎳膜之形成材料。 •使用Ni(PF2(CF3))4之矽化鎳膜之形成 使用圖1所示之CVD裝置，進行合成例1中獲得之 Ni(PF2(CF3))4之成膜評價。將Ni(PF2(CF3))4加入原料容 器中’使該容器維持在60 °C下，使作爲載體氣體之氨以 10毫升/分鐘之流量，作爲Si源之SiH4與H2之混合氣體 (SiH4 : H2 = (l : 9)(容積比））以20毫升/分鐘之流量流入， ® 導入反應容器中。此時，系統內減壓至20kPa，反應容器 內之基板溫度爲150〜3 5 0°C。 結果，確認基板上之膜堆積，以X射線光電子分析裝 置（XPS)(KRATOS製造之 AXIS-NOVA)調查膜之組成，確 認存在鎳及矽。又，確認幾乎沒有碳。接著由X射線繞射 裝置（XRD)(Rigaku製造之RAD-rX)之分析，確認該膜爲 矽化鎳膜。另外，自CVD裝置之排氣氣體分析確認幾乎 沒有HF。該排氣氣體之分析係以FT-IR(Thermoelectron 製造之Nicolet3 8 0)進行。 -15- 201026876 [實施例1-2] •使用Ni(PF2(CF3))4之鎳膜形成 除使用H2氣體取代SiH4與H2之混合氣體以外，餘 如實施例1 -1般成膜。結果，確認基板上之膜堆積，以X 射線光電子分析裝置（XPS)(KRATOS製造之 AXIS-NOVA) 調查膜之組成，確認存在鎳。又，確認幾乎沒有碳。接著 由X射線繞射裝置（XRD)(Rigaku製造之RAD-τ X)之分析， Θ 確認該膜爲鎳膜。另外，自CVD裝置之排氣氣體分析確認幾 乎沒有HF。該排氣氣體之分析係以FT-IR( Thermoelectron製 造之Nicolet3 80)進行。 [實施例2] • Ni(PF(CF3)2)4之成膜評價 針對合成例2中獲得之Ni(PF(CF3)2)4，使用示差熱熱 重量同時測定裝置（SII製造之TG/DTA6200)，求得加熱至 @ 5 00°C時之揮發率，爲99.6質量％。揮發殘留物極少。可 知適用作含鎳膜之形成材料。 [實施例2-1] •使用Ni(PF(CF3)2)4之矽化鎳膜之形成 除使用合成例2中獲得之Ni(PF(CF3)2)4，且原料容器Synthesis of Ni(PF2(CH3))4 This complex was synthesized according to the method described in Inorganic Chemistry, Vol. 4, vol., 65 1 (1 96S). First, 6.5 g of Ni(CO) 4 was placed in a 500 ml stainless steel pressure vessel, methyldifluorophosphine (24 g) was introduced, and after sealing, the vessel was heated at 150 ° C for 12 hours. After heating, the colorless liquid was fractionated by distillation. After analyzing the fractionated colorless liquid by GC-MS (JMS-AUTOMASSII manufactured by HP6890/JEOL manufactured by HP), ICP-AES (VISTA-PRO manufactured by SII), and an organic element analyzer (CHNS-932 manufactured by LECO), It was identified as Ni(PF2(CH3))4 (niobium (methyldifluorophosphine)) nickel) (1 1 g, yield 72%). -14-201026876 [Example 1] Evaluation of film formation of Ni(PF2(CF3))4 [Example 1-1] For Ni(PF2(CF3))4 obtained in Synthesis Example 1, differential heat of thermogravimetry was used. At the same time, the apparatus (TG/DTA6200 manufactured by SII) was measured, and the volatilization rate when heated to 500 ° C was determined to be 99.8 mass%. There are very few volatile residues, which can be used as a material for forming nickel-containing films. - Formation of Ni-Peposited Nickel Film Using Ni(PF2(CF3)) 4 The film formation evaluation of Ni (PF2(CF3))4 obtained in Synthesis Example 1 was carried out using the CVD apparatus shown in Fig. 1 . Ni(PF2(CF3))4 was added to the raw material container to maintain the container at 60 ° C, and the ammonia as a carrier gas was mixed at a flow rate of 10 ml/min as a Si source of SiH4 and H2 (SiH4). : H2 = (l : 9) (volume ratio)) flows in at a flow rate of 20 ml/min, and is introduced into the reaction vessel. At this time, the pressure in the system was reduced to 20 kPa, and the substrate temperature in the reaction vessel was 150 to 350 °C. As a result, the film deposition on the substrate was confirmed, and the composition of the film was examined by X-ray photoelectron analysis apparatus (XPS) (AXIS-NOVA manufactured by KRATOS) to confirm the presence of nickel and ruthenium. Also, it was confirmed that there was almost no carbon. Next, it was confirmed by an X-ray diffraction apparatus (XRD) (RAD-rX manufactured by Rigaku) that the film was a nickel telluride film. In addition, exhaust gas analysis from the CVD apparatus confirmed that there was almost no HF. The analysis of the exhaust gas was carried out by FT-IR (Nicolet 3 80 manufactured by Thermoelectron). -15-201026876 [Example 1-2] Formation of a nickel film using Ni (PF2(CF3)) 4 A film was formed as in Example 1-1, except that a mixed gas of SiH4 and H2 was replaced by H2 gas. As a result, the film deposition on the substrate was confirmed, and the composition of the film was examined by an X-ray photoelectron analyzer (XPS) (AXIS-NOVA manufactured by KRATOS) to confirm the presence of nickel. Also, it was confirmed that there was almost no carbon. Next, analysis by an X-ray diffraction apparatus (XRD) (RAD-τ X manufactured by Rigaku) confirmed that the film was a nickel film. In addition, exhaust gas analysis from the CVD apparatus confirmed that there was almost no HF. The analysis of the exhaust gas was carried out by FT-IR (Nicolet 3 80 manufactured by Thermoelectron). [Example 2] Evaluation of film formation of Ni(PF(CF3)2)4 For the Ni(PF(CF3)2)4 obtained in Synthesis Example 2, a differential thermogravimetric simultaneous measurement device (TG/SII manufactured by SII) was used. DTA6200), the volatilization rate when heated to @500 °C was found to be 99.6% by mass. Very little volatile residue. It is known to be suitable as a material for forming a nickel-containing film. [Example 2-1] Formation of a nickel-deposited nickel film using Ni (PF(CF3)2) 4 In addition to the use of Ni(PF(CF3)2)4 obtained in Synthesis Example 2, and a raw material container
之最初維持溫度爲8 0°C以外，餘如實施例1 -1般成膜。結 果，確認基板上之膜堆積，以X射線光電子分析裝置（XPS -16- 201026876 KKRATOS製造之AXIS-NOVA)調查膜之組成，確認存在 鎳及矽。又，確認幾乎沒有碳。接著由X射線繞射裝置 (XRD)(Rigaku製造之RAD- r X)之分析，確認該膜爲矽化鎳 膜。又，自CVD裝置之排氣氣體分析確認幾乎沒有HF。該 排氣氣體之分析係以FT-IR(Thermoelectron製造之Nicolet380) 進行。 [實施例2-2] •使用Ni(PF(CF3)2)4之鎳膜形成 除使用H2氣體取代SiH4與H2之混合氣體以外，餘 如實施例2-1般成膜。結果，確認基板上之膜堆積，以X 射線光電子分析裝置（XPS)(KRATOS製造之 AXIS-NOVA) 調査膜之組成，確認存在鎳。另外，確認幾乎沒有碳。接著 由X射線繞射裝置（XRD)(Rigaku製造之RAD- r X)之分析， 確認該膜爲鎳膜。又’自CVD裝置之排氣氣體分析確認幾 β 乎沒有HF。該排氣氣體之分析係以FT-IR( Thermoelectron 製造之Nicolet380)進行。 [實施例3] • Ni(PF2(CH3))4之成膜評價 針對合成例3中獲得之Ni(PF2(CH3))4，使用示差熱 熱重量同時測定裝置（SI1製造之TG/DTA6200)，求得加熱 至5 00 °C時之揮發率’爲99.5質量％。揮發殘留物極少。 可知係適用作含鎳膜之形成材料。 -17- 201026876 [實施例3-1] •使用Ni(PF2(CH3))4之矽化鎳膜形成 除使用合成例3中獲得之Ni(PF2(CH3))4以外，餘如 實施例1 -1般成膜。結果，確認基板上之膜堆積，以X射 線光電子分析裝置（XPS)(KRATOS製造之AXIS-NOVA)調 查膜之組成，確認存在鎳及矽。又，確認幾乎沒有碳。接 著由X射線繞射裝置（XRD)(Rigaku製造之RAD- r X)之分 0 析，確認該膜爲矽化鎳膜。另外，自CVD裝置之排氣氣 體分析確認幾乎沒有HF。該排氣氣體之分析係以FT-IR(Thermoelectron 製造之 Nicolet380)進行。 [實施例3-2] •使用Ni(PF2(CH3))4之鎳膜之形成 除使用H2氣體取代SiH4與H2之混合氣體以外，餘 如實施例3-1般成膜。結果，確認基板上之膜堆積，以X φ 射線光電子分析裝置（XPS)(KRATOS製造之 AXIS-NOVA) 調査膜之組成，確認存在鎳。另外，確認幾乎沒有碳。接著 由X射線繞射裝置（XRDKRigalcu製造之RAD-rX)之分析， 確認該膜爲鎳膜。又，自CVD裝置之排氣氣體分析確認幾 乎沒有HF。該排氣氣體之分析係以FT-IR( Thermoelectron 製造之Nicolet3 80)進行。 [比較例1 ] -18 - 201026876 • Ni(PF3)4之成膜評估 [比較例l-l] •使用Ni(PF3)4之矽化鎳膜之形成 除使用Ni(PF3)4，且使氦以20毫升/分鐘，作爲Si源 之8丨114與H2之混合氣體以50毫升/分鐘導入反應容器中 以外，餘如實施例1 -1般成膜。結果，確認基板上之膜堆 積，以 X射線光電子分析裝置（XPS)(KRATOS製造之 φ AXIS-NOVA)調查膜之組成，確認存在鎳及矽。又，確認 幾乎沒有碳。接著由X射線繞射裝置（XRD)(Rigaku製造 之RAD- 7Χ)之分析，確認該膜爲矽化鎳膜。然而，自 CVD裝置之排氣氣體分析確認副生成HF。該排氣氣體之 分析係以 FT-IR(Thermoelectron 製造之 Nicolet380)進行。 [比較例1 - 2 ] •使用Ni(PF3)4之鎳膜形成 β 除使用Η2氣體取代SiH4與Η2之混合氣體以外，餘 如比較例1 -1般成膜。其結果，確認基板上之膜堆積，以 X射線光電子分析裝置（XPS)(KRATOS製造之 AXIS-NOVA)調查膜之組成，確認存在鎳。又，確認幾乎沒有碳 。接著由X射線繞射裝置（XRD)(Rigaku製造之RAD - 7 X) 之分析，確認該膜爲鎳膜。然而，自CVD裝置之排氣氣 體分析確認副產生HF。該排氣氣體之分析係以FT-IR( Thermo electron 製造之 Nicolet380)進行。 -19- 201026876 【圖式簡單說明】 圖1爲CVD裝置之模式圖。 ❹The film was formed as in Example 1-1 except that the temperature was initially maintained at 80 °C. As a result, the film deposition on the substrate was confirmed, and the composition of the film was examined by an X-ray photoelectron analyzer (XXI-16-201026876 KKRATOS AXIS-NOVA) to confirm the presence of nickel and ruthenium. Also, it was confirmed that there was almost no carbon. Next, analysis by X-ray diffraction apparatus (XRD) (RAD-r X manufactured by Rigaku) confirmed that the film was a nickel telluride film. Further, the exhaust gas analysis from the CVD apparatus confirmed that there was almost no HF. The analysis of the exhaust gas was carried out by FT-IR (Nicolet 380 manufactured by Thermoelectron). [Example 2-2] Formation of nickel film using Ni (PF(CF3)2) 4 A film was formed as in Example 2-1, except that a mixed gas of SiH4 and H2 was replaced by H2 gas. As a result, the film deposition on the substrate was confirmed, and the composition of the film was examined by an X-ray photoelectron analyzer (XPS) (AXIS-NOVA manufactured by KRATOS) to confirm the presence of nickel. In addition, it is confirmed that there is almost no carbon. Next, it was confirmed by an X-ray diffraction apparatus (XRD) (RAD-r X manufactured by Rigaku) that the film was a nickel film. Further, the exhaust gas analysis from the CVD apparatus confirmed that there was no HF. The analysis of the exhaust gas was carried out by FT-IR (Nicolet 380 manufactured by Thermoelectron). [Example 3] Evaluation of film formation of Ni(PF2(CH3))4 For the Ni(PF2(CH3))4 obtained in Synthesis Example 3, a differential thermogravimetric simultaneous measurement device (TG/DTA6200 manufactured by SI1) was used. The volatilization rate at the time of heating to 500 ° C was determined to be 99.5% by mass. Very little volatile residue. It can be seen that it is suitable as a forming material for a nickel-containing film. -17-201026876 [Example 3-1] • Formation of a nickel-deposited nickel film using Ni(PF2(CH3)) 4 was carried out except that Ni(PF2(CH3))4 obtained in Synthesis Example 3 was used, and Example 1 was carried out. 1 film formation. As a result, the film deposition on the substrate was confirmed, and the composition of the film was examined by X-ray photoelectron analyzer (XPS) (AXIS-NOVA manufactured by KRATOS) to confirm the presence of nickel and ruthenium. Also, it was confirmed that there was almost no carbon. Subsequently, it was confirmed by an X-ray diffraction apparatus (XRD) (RAD-r X manufactured by Rigaku) that the film was a nickel-deposited nickel film. In addition, the exhaust gas analysis from the CVD apparatus confirmed that there was almost no HF. The analysis of the exhaust gas was carried out by FT-IR (Ninet Electron manufactured by Thermoelectron). [Example 3-2] Formation of a nickel film using Ni (PF2(CH3)) 4 A film was formed as in Example 3-1 except that a mixed gas of SiH4 and H2 was used instead of H2 gas. As a result, the film deposition on the substrate was confirmed, and the composition of the film was examined by X φ ray photoelectron analyzer (XPS) (AXIS-NOVA manufactured by KRATOS), and it was confirmed that nickel was present. In addition, it is confirmed that there is almost no carbon. Next, analysis by an X-ray diffraction apparatus (RAD-rX manufactured by XRDK Rigalcu) confirmed that the film was a nickel film. Further, the exhaust gas analysis from the CVD apparatus confirmed that there was almost no HF. The analysis of the exhaust gas was carried out by FT-IR (Nicolet 3 80 manufactured by Thermoelectron). [Comparative Example 1] -18 - 201026876 • Film formation evaluation of Ni(PF3)4 [Comparative Example ll] • Formation of a nickel-deposited nickel film using Ni(PF3)4, except that Ni(PF3)4 was used, and 氦 was made at 20 In a milliliter/minute, a mixed gas of 8丨114 and H2 as a Si source was introduced into the reaction vessel at 50 ml/min, and a film was formed as in Example 1-1. As a result, the film formation on the substrate was confirmed, and the composition of the film was examined by an X-ray photoelectron analyzer (XPS) (φ AXIS-NOVA manufactured by KRATOS) to confirm the presence of nickel and ruthenium. Also, it is confirmed that there is almost no carbon. Next, it was confirmed by an X-ray diffraction apparatus (XRD) (RAD-7 manufactured by Rigaku) that the film was a nickel telluride film. However, exhaust gas analysis from the CVD apparatus confirmed the generation of HF. The analysis of the exhaust gas was carried out by FT-IR (Ninet Electron manufactured by Thermoelectron). [Comparative Example 1 - 2] • Formation of a nickel film using Ni(PF3) 4 β A film was formed as in Comparative Example 1-1 except that a gas mixture of SiH4 and Η2 was used instead of the Η2 gas. As a result, the film deposition on the substrate was confirmed, and the composition of the film was examined by an X-ray photoelectron analyzer (XPS) (AXIS-NOVA manufactured by KRATOS) to confirm the presence of nickel. Also, confirm that there is almost no carbon. Next, it was confirmed by an X-ray diffraction apparatus (XRD) (RAD-7X manufactured by Rigaku) that the film was a nickel film. However, exhaust gas analysis from the CVD apparatus confirmed the generation of HF. The analysis of the exhaust gas was carried out by FT-IR (Ninetet 380 manufactured by Thermo Electron). -19- 201026876 [Simple description of the drawing] Fig. 1 is a schematic view of a CVD apparatus. ❹
-20--20-
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