JP6201204B2 - タングステン化合物を用いたタングステン−含有膜の蒸着方法及び前記タングステン化合物を含むタングステン−含有膜蒸着用前駆体組成物 - Google Patents
タングステン化合物を用いたタングステン−含有膜の蒸着方法及び前記タングステン化合物を含むタングステン−含有膜蒸着用前駆体組成物 Download PDFInfo
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- 229910052721 tungsten Inorganic materials 0.000 title claims description 98
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 title claims description 97
- 239000010937 tungsten Substances 0.000 title claims description 97
- 150000003658 tungsten compounds Chemical class 0.000 title claims description 59
- 238000000151 deposition Methods 0.000 title claims description 45
- 239000002243 precursor Substances 0.000 title claims description 42
- 239000000203 mixture Substances 0.000 title claims description 40
- 238000000034 method Methods 0.000 title claims description 22
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 142
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 92
- 239000007789 gas Substances 0.000 claims description 44
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 41
- 239000003381 stabilizer Substances 0.000 claims description 27
- 230000008021 deposition Effects 0.000 claims description 26
- 239000000758 substrate Substances 0.000 claims description 23
- 239000000463 material Substances 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 19
- 238000000231 atomic layer deposition Methods 0.000 claims description 19
- 238000005229 chemical vapour deposition Methods 0.000 claims description 18
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 15
- 239000003446 ligand Substances 0.000 claims description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- UGNWTBMOAKPKBL-UHFFFAOYSA-N tetrachloro-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(Cl)=C(Cl)C1=O UGNWTBMOAKPKBL-UHFFFAOYSA-N 0.000 claims description 8
- 125000004122 cyclic group Chemical group 0.000 claims description 7
- 239000012495 reaction gas Substances 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 6
- 238000007740 vapor deposition Methods 0.000 claims description 5
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- WAMKWBHYPYBEJY-UHFFFAOYSA-N duroquinone Chemical compound CC1=C(C)C(=O)C(C)=C(C)C1=O WAMKWBHYPYBEJY-UHFFFAOYSA-N 0.000 claims description 4
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 2
- 229910001882 dioxygen Inorganic materials 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- BWRULUWXPAWLAU-UHFFFAOYSA-N CC(C)(C)C1=CC=C(O)C(O)=C1.CC(C)(C)C1=CC=C(O)C(O)=C1 Chemical compound CC(C)(C)C1=CC=C(O)C(O)=C1.CC(C)(C)C1=CC=C(O)C(O)=C1 BWRULUWXPAWLAU-UHFFFAOYSA-N 0.000 claims 3
- HHEAADYXPMHMCT-UHFFFAOYSA-N dpph Chemical class [O-][N+](=O)C1=CC([N+](=O)[O-])=CC([N+]([O-])=O)=C1[N]N(C=1C=CC=CC=1)C1=CC=CC=C1 HHEAADYXPMHMCT-UHFFFAOYSA-N 0.000 claims 2
- 239000012528 membrane Substances 0.000 description 14
- XESZUVZBAMCAEJ-UHFFFAOYSA-N 4-tert-butylcatechol Chemical compound CC(C)(C)C1=CC=C(O)C(O)=C1 XESZUVZBAMCAEJ-UHFFFAOYSA-N 0.000 description 13
- 238000004519 manufacturing process Methods 0.000 description 13
- 238000002411 thermogravimetry Methods 0.000 description 13
- 150000001875 compounds Chemical class 0.000 description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 8
- 229910052710 silicon Inorganic materials 0.000 description 8
- 239000010703 silicon Substances 0.000 description 8
- 150000001345 alkine derivatives Chemical class 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 6
- 238000001000 micrograph Methods 0.000 description 6
- 150000002431 hydrogen Chemical class 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 125000002015 acyclic group Chemical group 0.000 description 4
- -1 alkyl nitrile Chemical class 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 3
- 229910052581 Si3N4 Inorganic materials 0.000 description 3
- 238000000113 differential scanning calorimetry Methods 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 3
- 238000009834 vaporization Methods 0.000 description 3
- 230000008016 vaporization Effects 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- BATMSLSJILEDGZ-UHFFFAOYSA-N carbon monoxide;hex-3-yne;tungsten Chemical compound [W].[O+]#[C-].CCC#CCC.CCC#CCC.CCC#CCC BATMSLSJILEDGZ-UHFFFAOYSA-N 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- JIGUICYYOYEXFS-UHFFFAOYSA-N 3-tert-butylbenzene-1,2-diol Chemical compound CC(C)(C)C1=CC=CC(O)=C1O JIGUICYYOYEXFS-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- FQNHWXHRAUXLFU-UHFFFAOYSA-N carbon monoxide;tungsten Chemical group [W].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-] FQNHWXHRAUXLFU-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- BOAMTGHGHLIYHH-UHFFFAOYSA-N cyclohexa-2,5-diene-1,4-dione Chemical compound O=C1C=CC(=O)C=C1.O=C1C=CC(=O)C=C1 BOAMTGHGHLIYHH-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000004442 gravimetric analysis Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002739 metals Chemical group 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- NXHILIPIEUBEPD-UHFFFAOYSA-H tungsten hexafluoride Chemical compound F[W](F)(F)(F)(F)F NXHILIPIEUBEPD-UHFFFAOYSA-H 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
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- 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
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F11/00—Compounds containing elements of Groups 6 or 16 of the Periodic Table
-
- 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
- C23C16/448—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials
- C23C16/4481—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials by evaporation using carrier gas in contact with the source material
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
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- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Chemical Vapour Deposition (AREA)
- Electrodes Of Semiconductors (AREA)
Description
タングステン前駆体化合物、トリス(3−へキシン)カルボニルタングステン[W(CO)(CH3CH2C≡CCH2CH3)3]は、知られた方法によって合成して得られた[Journal of the American Chemical Society(1963)、85(14)、2174]。得られたタングステン前駆体化合物に対して熱重量分析及び示差走査熱量計分析を行い、その結果は図1及び図2に示した。
前記製造例1で得られたトリス(3−へキシン)カルボニルタングステン[W(CO)(CH3CH2C≡CCH2CH3)3]気体と水素(H2)気体を相互に基材表面に接触させてタングステン−含有膜を形成した。基材としては、シリコン(Si)ウエハ、シリコン基材上に酸化シリコン(SiO2)膜が100nmの厚さで覆われたウエハ、シリコン基材上に窒化シリコン(SiN)膜が50nmの厚さで覆われたウエハ、及びシリコン基材上に窒化チタン(TiN)膜が50nm厚さで覆われたウエハそれぞれを用いた。このとき、前記基材の温度は325℃及び350℃でそれぞれ加熱し、前記製造例1で得られた化合物をステンレススチール(stainless steel)材質の容器に入れ、70℃の温度で前記容器を加熱しながら60sccm(1sccm=1.667×10−8m3/s)の流速を有するアルゴン気体を運搬気体として用い、前記製造例1で得られた化合物を気化させた。前記基材の平らな面に水平した方向に気体が流れる反応基の工程圧力は0.5torrに調節し、前記タングステン前駆体気体と水素気体を相互に原子層蒸着チャンバ内に置かれた前記基材に接触させた。前記水素気体は60sccmで流した。前記製造例1で得られた化合物気体供給20秒→Ar気体供給10秒→水素気体供給10秒→Ar気体供給10秒の気体供給周期を300回繰り返した後に形成されたタングステン−含有膜の断面を走査電子顕微鏡(SEM)で観察し、その結果を図3A〜図3D及び図4A〜図4Dに示した。
シリコン(Si)基材の温度は350℃で加熱し、前記製造例1で得られたタングステン化合物W(CO)(CH3CH2C≡CCH2CH3)3をステンレス鋼材質の容器に入れ、70℃の温度で容器を加熱しながら60sccmの流速を有するアルゴン気体を運搬気体として用い、前記製造例1で得られたタングステン−含有化合物を気化させた。反応基の工程圧力(working pressure)は0.5torr(1torr=133.3Pa)に調節し、前記製造例1で得られたタングステン化合物気体と水素気体またはアンモニア気体を相互に前記実施例1のような反応基の内に置かれた前記シリコン基材に接触させた。前記水素気体または前記アンモニア気体は500sccmの流速で流した。前記製造例1で得られた化合物気体供給10秒→Ar気体供給10秒→水素気体またはアンモニア気体供給20秒→Ar気体供給10秒の気体供給周期を300回繰り返すことで、タングステン−含有膜を形成した。以後、オージェ分光器を用いて前記形成されたタングステン−含有膜の深さによる炭素、窒素、酸素及びタングステンの含量を分析し、図5及び図6に示した。
CVDまたはALDの目的で用いられる前駆体組成物の安全性を向上させるために、前記製造例1で製造されたタングステン化合物W(CO)(CH3CH2C≡CCH2CH3)3に4−tert−butylcatechol(TBC)を3,000ppm添加した、タングステン−含有膜蒸着用前駆体組成物の熱重量分析(TGA)を実施した。
Claims (15)
- 前記Lは、一酸化炭素(CO)、一酸化窒素(NO)、及びアセトニトリル(CH3CN)からなる群より選択されるいずれか一つである、請求項1に記載のタングステン−含有膜の蒸着方法。
- 前記タングステン化合物は、W(CO)(HC≡CH)3、W(CO)(CH3C≡CCH3)3、W(CO)(CH3CH2C≡CCH2CH3)3、W(CO)(CH3(CH2)2C≡C(CH2)2CH3)3、W(CO)(HC≡CCH3)3、W(CO)(HC≡CCH2CH3)3、W(CO)(HC≡C(CH2)2CH3)3、W(CO)(HC≡C(CH2)3CH3)3、W(CO)(HC≡C(CH2)4CH3)3、W(CO)(CH3C≡CCH2CH3)3、W(CO)(CH3C≡C(CH2)2CH3)3、W(CO)(CH3C≡C(CH2)3CH3)3、W(CO)(CH3CH2C≡C(CH2)2CH3)3、W(CO)(HC≡CCH(CH3)2)3、W(CO)(HC≡CC(CH3)3)3、W(CO)(HC≡C(CH2CH(CH3)2)3、W(NO)(HC≡CH)3、W(NO)(CH3C≡CCH3)3、W(NO)(CH3CH2C≡CCH2CH3)3、W(NO)(CH3(CH2)2C≡C(CH2)2CH3)3、W(NO)(HC≡CCH3)3、W(NO)(HC≡CCH2CH3)3、W(NO)(HC≡C(CH2)2CH3)3、W(NO)(HC≡C(CH2)3CH3)3、W(NO)(HC≡C(CH2)4CH3)3、W(NO)(CH3C≡CCH2CH3)3、W(NO)(CH3C≡C(CH2)2CH3)3、W(NO)(CH3C≡C(CH2)3CH3)3、W(NO)(CH3CH2C≡C(CH2)2CH3)3、W(NO)(HC≡CCH(CH3)2)3、W(NO)(HC≡CC(CH3)3)3、W(NO)(HC≡C(CH2CH(CH3)2)3、W(CH3CN)(HC≡CH)3、W(CH3CN)(CH3C≡CCH3)3、W(CH3CN)(CH3CH2C≡CCH2CH3)3、W(CH3CN)(CH3(CH2)2C≡C(CH2)2CH3)3、W(CH3CN)(HC≡CCH3)3、W(CH3CN)(HC≡CCH2CH3)3、W(CH3CN)(HC≡C(CH2)2CH3)3、W(CH3CN)(HC≡C(CH2)3CH3)3、W(CH3CN)(HC≡C(CH2)4CH3)3、W(CH3CN)(CH3C≡CCH2CH3)3、W(CH3CN)(CH3C≡C(CH2)2CH3)3、W(CH3CN)(CH3C≡C(CH2)3CH3)3、W(CH3CN)(CH3CH2C≡C(CH2)2CH3)3、W(CH3CN)(HC≡CCH(CH3)2)3、W(CH3CN)(HC≡CC(CH3)3)3、及びW(CH3CN)(HC≡C(CH2CH(CH3)2)3からなる群より選択されるいずれか一つである、請求項1または2に記載のタングステン−含有膜の蒸着方法。
- 前記タングステン化合物がW(CO)(CH3CH2C≡CCH2CH3)3 である、請求項1または2に記載のタングステン−含有膜の蒸着方法。
- 前記タングステン−含有膜を蒸着することは、前記タングステン化合物を含む気体を前記基材に接触させると共に、または相互に水素気体、アンモニア気体、酸素気体またはオゾン気体を含有する反応気体を前記基材に接触させることをさらに含む、請求項1から4のいずれか一項に記載のタングステン−含有膜の蒸着方法。
- 前記タングステン−含有膜を蒸着することは、有機金属化学気相蒸着法(MOCVD)または原子層蒸着法(ALD)により行われる、請求項1から4のいずれか一項に記載のタングステン−含有膜の蒸着方法。
- 前記タングステン化合物を含む気体が前記タングステン化合物の熱分解を抑制する安定剤をさらに含むものである、請求項1から6のいずれか一項に記載のタングステン−含有膜の蒸着方法。
- 前記安定剤は、ベンゾキノン(benzoquinone)、テトラメチルベンゾキノン(tetramethylbenzoquinone)、クロラニル(chloranil、2,3,5,6−tetrachloro−1,4−benzoquinone)、4−tert−ブチルカテコール(4−tert−butylcatechol)、及び2,2−ジフェニル−1−ピクリルヒドラジル(2,2−diphenyl−1−picrylhydrazyl)からなる群より選択される一つ以上である、請求項7に記載のタングステン−含有膜の蒸着方法。
- 前記Lは一酸化炭素(CO)、一酸化窒素(NO)、及びアセトニトリル(CH3CN)からなる群より選択されるいずれか一つである、請求項9に記載のタングステン−含有膜蒸着用前駆体組成物。
- 前記タングステン化合物は、W(CO)(HC≡CH)3、W(CO)(CH3C≡CCH3)3、W(CO)(CH3CH2C≡CCH2CH3)3、W(CO)(CH3(CH2)2C≡C(CH2)2CH3)3、W(CO)(HC≡CCH3)3、W(CO)(HC≡CCH2CH3)3、W(CO)(HC≡C(CH2)2CH3)3、W(CO)(HC≡C(CH2)3CH3)3、W(CO)(HC≡C(CH2)4CH3)3、W(CO)(CH3C≡CCH2CH3)3、W(CO)(CH3C≡C(CH2)2CH3)3、W(CO)(CH3C≡C(CH2)3CH3)3、W(CO)(CH3CH2C≡C(CH2)2CH3)3、W(CO)(HC≡CCH(CH3)2)3、W(CO)(HC≡CC(CH3)3)3、W(CO)(HC≡C(CH2CH(CH3)2)3、W(NO)(HC≡CH)3、W(NO)(CH3C≡CCH3)3、W(NO)(CH3CH2C≡CCH2CH3)3、W(NO)(CH3(CH2)2C≡C(CH2)2CH3)3、W(NO)(HC≡CCH3)3、W(NO)(HC≡CCH2CH3)3、W(NO)(HC≡C(CH2)2CH3)3、W(NO)(HC≡C(CH2)3CH3)3、W(NO)(HC≡C(CH2)4CH3)3、W(NO)(CH3C≡CCH2CH3)3、W(NO)(CH3C≡C(CH2)2CH3)3、W(NO)(CH3C≡C(CH2)3CH3)3、W(NO)(CH3CH2C≡C(CH2)2CH3)3、W(NO)(HC≡CCH(CH3)2)3、W(NO)(HC≡CC(CH3)3)3、W(NO)(HC≡C(CH2CH(CH3)2)3、W(CH3CN)(HC≡CH)3、W(CH3CN)(CH3C≡CCH3)3、W(CH3CN)(CH3CH2C≡CCH2CH3)3、W(CH3CN)(CH3(CH2)2C≡C(CH2)2CH3)3、W(CH3CN)(HC≡CCH3)3、W(CH3CN)(HC≡CCH2CH3)3、W(CH3CN)(HC≡C(CH2)2CH3)3、W(CH3CN)(HC≡C(CH2)3CH3)3、W(CH3CN)(HC≡C(CH2)4CH3)3、W(CH3CN)(CH3C≡CCH2CH3)3、W(CH3CN)(CH3C≡C(CH2)2CH3)3、W(CH3CN)(CH3C≡C(CH2)3CH3)3、W(CH3CN)(CH3CH2C≡C(CH2)2CH3)3、W(CH3CN)(HC≡CCH(CH3)2)3、W(CH3CN)(HC≡CC(CH3)3)3、及びW(CH3CN)(HC≡C(CH2CH(CH3)2)3からなる群より選択されるいずれか一つである、請求項9または10に記載のタングステン−含有膜蒸着用前駆体組成物。
- 前記タングステン化合物がW(CO)(CH3CH2C≡CCH2CH3)3 である、請求項9または10に記載のタングステン−含有膜蒸着用前駆体組成物。
- 前記タングステン化合物の熱分解を抑制する安定剤をさらに含む、請求項9から12のいずれか一項に記載のタングステン−含有膜蒸着用前駆体組成物。
- 前記安定剤は、ベンゾキノン(benzoquinone)、テトラメチルベンゾキノン(tetramethylbenzoquinone)、クロラニル(chloranil、2,3,5,6−tetrachloro−1,4−benzoquinone)、4−tert−ブチルカテコール(4−tert−butylcatechol)、及び2,2−ジフェニル−1−ピクリルヒドラジル(2,2−diphenyl−1−picrylhydrazyl)からなる群より選択される一つ以上である、請求項13に記載のタングステン−含有膜蒸着用前駆体組成物。
- 前記タングステン化合物がW(CO)(CH3CH2C≡CCH2CH3)3 であり、
前記安定剤が4−tert−ブチルカテコール(4−tert−butylcatechol)である、請求項13に記載のタングステン−含有膜蒸着用前駆体組成物。
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