WO2012132669A1 - ユーロピウム含有薄膜形成用前駆体及びユーロピウム含有薄膜の形成方法 - Google Patents
ユーロピウム含有薄膜形成用前駆体及びユーロピウム含有薄膜の形成方法 Download PDFInfo
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- WO2012132669A1 WO2012132669A1 PCT/JP2012/054388 JP2012054388W WO2012132669A1 WO 2012132669 A1 WO2012132669 A1 WO 2012132669A1 JP 2012054388 W JP2012054388 W JP 2012054388W WO 2012132669 A1 WO2012132669 A1 WO 2012132669A1
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- europium
- thin film
- containing thin
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- 229910052693 Europium Inorganic materials 0.000 title claims abstract description 44
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 37
- 239000010409 thin film Substances 0.000 title claims abstract description 29
- 239000002243 precursor Substances 0.000 title claims abstract description 25
- 230000015572 biosynthetic process Effects 0.000 title abstract description 25
- 238000000231 atomic layer deposition Methods 0.000 claims abstract description 27
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 16
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims 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 claims description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 230000008018 melting Effects 0.000 abstract description 19
- 238000002844 melting Methods 0.000 abstract description 19
- 150000002178 europium compounds Chemical class 0.000 abstract description 13
- 230000005587 bubbling Effects 0.000 abstract description 10
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 abstract description 6
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 abstract description 4
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 abstract 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 24
- 239000010408 film Substances 0.000 description 22
- 238000005259 measurement Methods 0.000 description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 11
- 239000001301 oxygen Substances 0.000 description 11
- 229910052760 oxygen Inorganic materials 0.000 description 11
- 239000007787 solid Substances 0.000 description 11
- 239000002904 solvent Substances 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 11
- 238000004821 distillation Methods 0.000 description 10
- 239000002994 raw material Substances 0.000 description 10
- 239000007800 oxidant agent Substances 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Substances C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 239000000523 sample Substances 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- -1 cyclopentadienyl compound Chemical class 0.000 description 5
- 238000002451 electron ionisation mass spectrometry Methods 0.000 description 5
- RHXUZKJNHAMZEP-LWTKGLMZSA-N europium;(z)-5-hydroxy-2,2,6,6-tetramethylhept-4-en-3-one Chemical compound [Eu].CC(C)(C)C(\O)=C\C(=O)C(C)(C)C.CC(C)(C)C(\O)=C\C(=O)C(C)(C)C.CC(C)(C)C(\O)=C\C(=O)C(C)(C)C RHXUZKJNHAMZEP-LWTKGLMZSA-N 0.000 description 5
- 230000009257 reactivity Effects 0.000 description 5
- 239000007789 gas Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 150000004767 nitrides Chemical class 0.000 description 4
- 238000010926 purge Methods 0.000 description 4
- 238000009834 vaporization Methods 0.000 description 4
- 230000008016 vaporization Effects 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 3
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 229910000102 alkali metal hydride Inorganic materials 0.000 description 2
- 150000008046 alkali metal hydrides Chemical class 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
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- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000001577 simple distillation Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000000859 sublimation Methods 0.000 description 2
- 230000008022 sublimation Effects 0.000 description 2
- 238000005092 sublimation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 150000003613 toluenes Chemical class 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- NKBSIBTVPNHSIK-UHFFFAOYSA-N 2,3-dichloro-6,7-dimethylquinoxaline Chemical compound ClC1=C(Cl)N=C2C=C(C)C(C)=CC2=N1 NKBSIBTVPNHSIK-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000000538 analytical sample Substances 0.000 description 1
- PSBUJOCDKOWAGJ-UHFFFAOYSA-N azanylidyneeuropium Chemical compound [Eu]#N PSBUJOCDKOWAGJ-UHFFFAOYSA-N 0.000 description 1
- 150000001722 carbon compounds Chemical class 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 150000001793 charged compounds Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- CFDPEPOXSGIPDG-UHFFFAOYSA-N cyclopenta-1,3-diene;europium(3+) Chemical compound [Eu+3].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 CFDPEPOXSGIPDG-UHFFFAOYSA-N 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000000752 ionisation method Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000005121 nitriding Methods 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
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- 150000003568 thioethers Chemical class 0.000 description 1
- 239000006200 vaporizer Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Images
Classifications
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- 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
- C07F17/00—Metallocenes
-
- 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
- H01L29/40—Electrodes ; Multistep manufacturing processes therefor
- H01L29/43—Electrodes ; Multistep manufacturing processes therefor characterised by the materials of which they are formed
- H01L29/49—Metal-insulator-semiconductor electrodes, e.g. gates of MOSFET
- H01L29/51—Insulating materials associated therewith
- H01L29/517—Insulating materials associated therewith the insulating material comprising a metallic compound, e.g. metal oxide, metal silicate
-
- 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
- C23C16/34—Nitrides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
- C23C16/45553—Atomic layer deposition [ALD] characterized by the use of precursors specially adapted for ALD
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
-
- 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
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
- H01L21/02172—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides
- H01L21/02175—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal
- H01L21/02192—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal the material containing at least one rare earth metal element, e.g. oxides of lanthanides, scandium or yttrium
-
- 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
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
- H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
- H01L21/02263—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase
- H01L21/02271—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition
Definitions
- the present invention relates to a precursor suitable for forming a europium-containing thin film as a gate insulating film or an optical material thin film, and a method for forming a europium-containing thin film using the same.
- a thin film containing europium As a thin film containing europium, a thin film in which europium is added to a gate insulating film or an optical material has been known (for example, see Patent Document 1 and Non-Patent Document 1).
- dpm trisuji Pivaloylmethanato europium
- Eu (hfac) 3 europium fluorinated ⁇ -diketonate
- Patent Document 1 discloses tricyclopentadienyl europium (hereinafter abbreviated as Eu (Cp) 3 ), which is a trivalent cyclopentadienyl compound, and Eu, which is a divalent cyclopentadienyl compound.
- Eu (Cp) 3 tricyclopentadienyl europium
- Eu which is a divalent cyclopentadienyl compound. The film formation using [C 5 (CH 3 ) 5 ] 2 is described.
- raw material containers and pipes used in the CVD method and ALD method are set to 180 ° C. or less because of heat resistance problems such as valves.
- Eu (dpm) 3 has a high melting point of 187 to 189 ° C. with respect to a vapor pressure of 0.1 torr / 180 ° C. Therefore, when this precursor is supplied into the film forming apparatus, it needs to be sublimated and supplied.
- the supply amount by the sublimation method changes depending on the shape of the solid in the raw material container, and the shape changes with the supply, so that stable supply is difficult.
- the piping from the raw material container to the chamber must be maintained at a temperature about 20 ° C.
- Eu (hfac) 3 as compared to Eu (dpm) 3, high vapor pressure, the raw material supply easily, but for others, had similar problems and Eu (dpm) 3.
- ⁇ -diketonate compounds such as Eu (dpm) 3 and Eu (hfac) 3 contain oxygen in the molecule, and thus can basically be used only for forming an oxide film.
- the trivalent cyclopentadienyl-based europium compound is unstable to heat and decomposes in the raw material container or vaporizer, so that it cannot be used in the CVD method or the ALD method.
- Eu [C 5 (CH 3 ) 5 ] 2 which is a divalent cyclopentadienyl-based europium compound, has a high melting point of 211 ° C., and therefore needs to be supplied by a sublimation method, which is also Eu (dpm ) Similar to 3 , there was a problem in terms of supply stability.
- the conventional europium precursor as described above sublimes without being liquefied due to the relationship between the melting point and the vapor pressure, so that it is difficult to carry out distillation purification and it is difficult to obtain a high-purity one. It was.
- the europium precursor for film formation has been required to have high thermal stability, a melting point of 180 ° C. or less, and be able to be stably supplied by bubbling.
- water can be used as an oxidant, can be purified by distillation, does not contain oxygen, and can form a nitride or sulfide film.
- the present inventors have repeatedly investigated a europium precursor suitable for forming a europium-containing thin film by a CVD method or an ALD method.
- a divalent cyclopentadienyl-based europium compound has been It is considered to be promising as a europium precursor in CVD and ALD because it is stable with respect to water and reacts quickly with water, improving the conventionally known Eu [C 5 (CH 3 ) 5 ] 2 And found a novel europium compound.
- the present invention uses a novel europium compound having a melting point of 180 ° C. or less and can be stably supplied by bubbling in a CVD method or an ALD method, a precursor for forming a europium-containing thin film, and a precursor thereof. It is an object of the present invention to provide a method for forming a europium-containing thin film.
- a novel europium compound bis (tetramethylmonoalkylcyclo) represented by Eu [C 5 (CH 3 ) 4 R] 2 (wherein R is an alkyl group having 2 or more carbon atoms). Pentadienyl) europium is provided. So far, there is no report on the synthesis or physical properties of Eu [C 5 (CH 3 ) 4 R] 2 , and this europium compound is a new chemical substance.
- R in Eu [C 5 (CH 3 ) 4 R] 2 is preferably an alkyl group having 2 to 5 carbon atoms. More preferably, they are any of an ethyl group, an n-propyl group, an n-butyl group, and an n-pentyl group. That is, Eu [C 5 (CH 3 ) 4 R] 2 includes Eu [C 5 (CH 3 ) 4 (C 2 H 5 )] 2 , Eu [C 5 (CH 3 ) 4 (n-C 3 H). 7)] 2, Eu [C 5 (CH 3) 4 (n-C 4 H 9)] 2 , and Eu [C 5 (CH 3) 4 (n-C 5 H 11)] 2 that is either Is more preferable.
- Eu [C 5 (CH 3) 4 R] europium-containing thin film-forming precursors by CVD or ALD by 2 is provided.
- Eu [C 5 (CH 3 ) 4 R] 2 has a melting point of 180 ° C. or less, can be supplied by bubbling, and can be a suitable precursor for forming a europium-containing thin film by a CVD method or an ALD method.
- the formation method of the europium containing thin film using the said precursor for europium containing thin film formation is provided.
- Eu [C 5 (CH 3 ) 4 R] 2 can be suitably used for forming a europium-containing thin film by a CVD method or an ALD method.
- Eu [C 5 (CH 3 ) 4 R] 2 is a novel europium compound, and has excellent heat stability and melting point compared to the europium compound used as a conventional europium-containing thin film precursor. Is 180 ° C. or lower, and stable supply by bubbling is possible. In addition, since the reactivity with the oxidizing agent is high and water can be used as the oxidizing agent, the film hardly contains carbon. Furthermore, since it can be purified by distillation, it has the advantages of being easily purified and excellent in mass productivity. Therefore, Eu [C 5 (CH 3 ) 4 R] 2 is a europium compound suitable as a precursor for forming a europium-containing thin film by a CVD method or an ALD method. Since Eu [C 5 (CH 3 ) 4 R] 2 does not contain oxygen in the molecule, a europium-containing thin film that does not contain oxygen such as nitrides and sulfides can be suitably formed.
- FIG. 2 is an electron ionization mass spectrometry (EI-MS) spectrum of the sample (Eu [C 5 (CH 3 ) 4 (nC 3 H 7 )] 2 ) obtained in Example 1.
- FIG. 3 is a diagram (TG-DTA curve) showing a differential thermothermogravimetric measurement result of a sample (Eu [C 5 (CH 3 ) 4 (nC 3 H 7 )] 2 ) obtained in Example 1. Is a sample obtained in Example 3 (Eu [C 5 (CH 3) 4 (C 2 H 5)] 2) shows a differential thermogravimetric measurement results of (TG-DTA curve).
- Eu [C 5 (CH 3 ) 4 R] 2 is a novel europium compound that has not been reported so far with respect to synthesis and physical properties. Therefore, this compound has a melting point of 180 ° C. or less, can be supplied by bubbling in the CVD method or the ALD method, and has not been known to be a precursor for forming a europium-containing thin film.
- the first production method is a method of reacting metal Eu with tetramethylmonoalkylcyclopentadiene (hereinafter referred to as C 5 (CH 3 ) 4 RH) in liquid ammonia.
- the reaction solvent includes diethyl ether, tethydrofuran (hereinafter abbreviated as THF), ethers such as dibutyl ether, saturated fatty hydrocarbons such as pentane, hexane, and octane, and aromatics such as benzene, toluene, and xylene. Hydrocarbons can be used alone or in admixture.
- a solvent containing toluene having high solubility of liquid ammonia is used.
- the reaction temperature is a temperature at which ammonia can exist as a liquid, and preferably a temperature slightly lower than the boiling point of ammonia when the reaction is at normal pressure.
- ether is added to dissolve the product as an ether adduct, and the unreacted product is separated by filtration. Then, the filtrate is distilled off at 60 to 200 ° C. under reduced pressure to remove the solvent and added ether, whereby a crude product of Eu [C 5 (CH 3 ) 4 R] 2 is obtained.
- alkali metal hydride and C 5 (CH 3 ) 4 RH are reacted to synthesize MC 5 (CH 3 ) 4 R (where M is an alkali metal element), and this is dried with EuI.
- the alkali metal hydride NaH or KH can be used. LiH is not preferable because the reaction does not proceed completely.
- Anhydrous EuI 2 preferably has a water content of 100 ppm or less.
- a reaction solvent at this time a solvent containing ether such as diethyl ether, THF, dibutyl ether or the like can be used. After the reaction, the solvent is replaced with an extraction solvent, and unreacted substances are separated by filtration.
- the extraction solvent a mixed solvent of ethers and saturated aliphatic hydrocarbons or aromatic hydrocarbons is used.
- a mixed solvent of THF and toluene is used.
- the filtrate is distilled off at 60 to 200 ° C. under reduced pressure to remove the solvent and added ether, whereby a crude product of Eu [C 5 (CH 3 ) 4 R] 2 is obtained. It should be noted that, in any of the above two synthesis methods, if the filtrate is not completely distilled off, the ether is not completely eliminated from the ether adduct.
- the crude Eu [C 5 (CH 3 ) 4 R] 2 obtained by the above synthesis method is distilled at 160 to 230 ° C. and 0.001 to 1 torr to obtain high purity Eu [C 5 (CH 3 ) 4 R]. 2 is obtained as a fraction.
- the melting point of Eu [C 5 (CH 3 ) 4 (C 2 H 5 )] 2 is 122.4 ° C., and the melting point of Eu [C 5 (CH 3 ) 4 (nC 3 H 7 )] 2 is 49.1.
- Eu [C 5 (CH 3 ) 4 (n-C 4 H 9 )] 2 has a melting point of 31.7 ° C.
- Eu [C 5 (CH 3 ) 4 (n-C 5 H 11 )] 2 is room temperature It is a highly viscous liquid.
- the portion for cooling and collecting the fraction is preferably about 55 to 130 ° C.
- the distillation is preferably repeated twice or more in order to completely remove the slightly added ether.
- Eu [C 5 (CH 3 ) 4 R] 2 obtained by the above method as a raw material for film formation (precursor), a europium-containing oxide, nitride, Sulfide can be suitably formed.
- Eu [C 5 (CH 3 ) 4 R] 2 is heated to 100 to 180 ° C. to obtain a fluid liquid. Vaporization by bubbling a carrier gas, or Eu [C 5 (CH 3 ) 4 R] 2 dissolved in an inert hydrocarbon solvent and supplied by a liquid mass flow meter, vaporization at 170 to 350 ° C.
- an aromatic hydrocarbon having a relatively high solubility is preferable, and a high boiling point solvent such as tetralin is particularly preferable.
- Eu 2 O 3 is formed by CVD or ALD.
- a film can be formed. If a vapor of Eu [C 5 (CH 3 ) 4 R] 2 and a nitride such as ammonia or hydrazine are used as a nitriding agent, a europium nitride film can be formed by a CVD method or an ALD method.
- a europium sulfide film can be formed by a CVD method or an ALD method.
- Eu [C 5 (CH 3 ) 4 (n-C 3 H 7 )] 2 does not undergo thermal degradation in a short time on the order of minutes at 350 ° C. or lower, and is a raw material for ALD and CVD methods. Therefore, it can be said that it has the thermal stability required.
- Vapor pressure As a result of measurement by the gas saturation method, it was 0.1 torr / 161 ° C.
- Example 3 Formation of Eu 2 O 3 film by ALD method using Eu [C 5 (CH 3 ) 4 (n-C 3 H 7 )] 2 Eu [C 5 (CH 3 ) 4 (n-C 3 H 7 )] 2 Bubbling with 100 sccm of Ar gas (A pulse) while heating the cylinder filled with 30 g to 170 ° C., while heating the cylinder filled with water to 20 ° C. Then, bubbling was performed with 50 sccm of Ar gas (B pulse), Ar 200 sccm was passed as the purge gas, and ALD operation was performed with each pulse being introduced for 1 second and purge being 3 seconds. An Si substrate with a substrate temperature of 300 ° C.
- Example 4 Synthesis of Eu [C 5 (CH 3 ) 4 (C 2 H 5 )] 2 Instead of C 5 (CH 3 ) 4 (n-C 3 H 7 ) H, C 5 (CH 3 ) The synthesis was performed in the same manner as in Example 1 except that 4 (C 2 H 5 ) H was used. Eu [C 5 (CH 3 ) 4 (C 2 H 5 )] was obtained in a yield of 53.5%. 2 was obtained. It was a solid that immediately decomposed when exposed to moisture and oxygen in the atmosphere. The vapor pressure observed during the distillation operation was 0.02 torr / 152 ° C. FIG. 3 shows the TG-DTA measurement results. As shown in FIG. 3, a melting point was observed at 122.4 ° C.
- this compound has properties suitable as a precursor for forming europium-containing thin films by CVD or ALD methods. It was recognized that
- Example 5 Synthesis of Eu [C 5 (CH 3 ) 4 (n-C 4 H 9 )] 2 Instead of C 5 (CH 3 ) 4 (n-C 3 H 7 ) H, C 5 (CH 3 ) Synthesis was carried out in the same manner as in Example 1 except that 4 (nC 4 H 9 ) H was used. Eu [C 5 (CH 3 ) 4 (n— C 4 H 9)] 2 were obtained. It was a solid that immediately decomposed when exposed to moisture and oxygen in the atmosphere. The vapor pressure observed during the distillation operation was 0.25 torr / 172 ° C. FIG. 4 shows the TG-DTA measurement results. As shown in FIG. 4, a melting point was observed at 31.7 ° C.
- this compound has properties suitable as a precursor for forming europium-containing thin films by CVD or ALD methods. It was recognized that
- Example 6 Synthesis of Eu [C 5 (CH 3 ) 4 (n-C 5 H 11 )] 2 Instead of C 5 (CH 3 ) 4 (n-C 3 H 7 ) H, C 5 (CH 3 ) Synthesis was carried out in the same manner as in Example 1 except that 4 (n-C 5 H 11 ) H was used. As a result, Eu [C 5 (CH 3 ) 4 (n- C 5 H 11 )] 2 was obtained. It is a highly viscous liquid at room temperature and immediately decomposed when exposed to atmospheric moisture and oxygen. The vapor pressure observed during the distillation operation was 0.01 torr / 155 ° C.
- FIG. 5 shows the TG-DTA measurement results. As shown in FIG.
- FIG. 6 shows the TG-DTA measurement results. As shown in FIG. 6, a melting point was observed at 211.2 ° C. As can be seen from this result, the present compound is difficult to supply by bubbling and is difficult to purify by distillation.
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Abstract
Description
このようなユーロピウム含有薄膜を化学的気相成長法(以下、CVD法と略記する)や原子層堆積法(以下、ALD法と略記する)により形成する際に用いられる前駆体としては、トリスジピバロイルメタナトユーロピウム(以下、Eu(dpm)3と略記する)やユーロピウムフッ素化β-ジケトナート(以下、Eu(hfac)3と略記する)が知られていた(非特許文献2参照)。
しかしながら、Eu(dpm)3は、蒸気圧0.1torr/180℃に対して、融点が187~189℃と高い。そのため、この前駆体を成膜装置内に供給する場合、昇華させて供給する必要があった。昇華法による供給量は原料容器内の固体の形状により変化し、その形状は供給とともに変化するため、安定的な供給が困難であった。
また、原料の固化による配管の閉塞を防ぐために、原料容器からチャンバまでの配管を原料容器よりも20℃程度高い温度に保持しなければならない。
また、ALD法による成膜においては、基板温度と同程度の300℃程度で熱分解するため、原子層堆積以外のメカニズムでの成膜が生じ、不純物を含んだ膜が形成されやすいという問題を有していた。さらに、水との反応性が低いため、酸化剤に水が適さない。このため、酸化剤にO3を用いる必要があるが、dpm基の分解により生じた炭素化合物が膜中に混入しやすいという問題もあった。
また、Eu(dpm)3やEu(hfac)3のようなβ-ジケトナート系化合物は分子中に酸素を含むため、基本的に酸化物膜の形成にしか用いることができなかった。
また、二価のシクロペンタジエニル系ユーロピウム化合物であるEu[C5(CH3)5]2は、融点が211℃と高いため、昇華法により供給する必要があり、これも、Eu(dpm)3と同様に、供給安定性の点で問題があった。
これまでに、Eu[C5(CH3)4R]2の合成や物性に関する報告はないことから、このユーロピウム化合物は新規化学物質である。
より好ましくは、エチル基、n-プロピル基、n-ブチル基及びn-ペンチル基のうちのいずれかである。すなわち、前記Eu[C5(CH3)4R]2は、Eu[C5(CH3)4(C2H5)]2、Eu[C5(CH3)4(n-C3H7)]2、Eu[C5(CH3)4(n-C4H9)]2及びEu[C5(CH3)4(n-C5H11)]2のいずれかであることがより好ましい。
Eu[C5(CH3)4R]2は、融点が180℃以下であり、バブリングによる材料供給が可能であり、CVD法やALD法によるユーロピウム含有薄膜形成に好適な前駆体となり得る。
上記のように、Eu[C5(CH3)4R]2は、CVD法やALD法によるユーロピウム含有薄膜の形成に好適に用いることができる。
したがって、Eu[C5(CH3)4R]2は、CVD法やALD法によるユーロピウム含有薄膜形成用の前駆体として好適なユーロピウム化合物である。また、Eu[C5(CH3)4R]2は分子中に酸素を含まないため、窒化物や硫化物等の酸素を含まないユーロピウム含有薄膜を好適に形成することができる。
本発明に係るEu[C5(CH3)4R]2は、これまでに合成や物性に関する報告がなされていない新規のユーロピウム化合物である。したがって、この化合物は、融点が180℃以下であり、CVD法やALD法においてバブリングで供給可能であり、ユーロピウム含有薄膜形成用の前駆体となり得ることは知られていなかった。
第1の製造方法は、液体アンモニア中で金属Euとテトラメチルモノアルキルシクロペンタジエン(以下、C5(CH3)4RHと表記する)を反応させる方法である。
このとき、反応溶媒としては、ジエチルエーテル、テトヒドロフラン(以下、THFと略記する)、ジブチルエーテル等のエーテル、ペンタン、ヘキサン、オクタン等の飽和脂肪炭化水素、ベンゼン、トルエン、キシレン等の芳香族炭化水素を、単独又は混合して使用することができる。好ましくは、液体アンモニアの溶解度が高いトルエンを含む溶媒が用いられる。
反応温度は、アンモニアが液体で存在可能な温度とし、好ましくは、反応が常圧の場合、アンモニアの沸点よりもわずかに低い温度とする。
反応後、エーテルを加えて生成物をエーテル付加物として溶解させた後、未反応物をろ過分離する。そして、減圧下、60~200℃でろ液を留去して、溶媒と付加しているエーテルを除去することにより、Eu[C5(CH3)4R]2の粗製物が得られる。
水素化アルカリ金属としては、NaH又はKHを用いることができる。LiHは反応が完全に進行しないため、好ましくない。
無水EuI2は、水分量が100ppm以下であることが好ましい。
このときの反応溶媒としては、ジエチルエーテル、THF、ジブチルエーテル等のエーテルを含む溶媒を使用することができる。
反応後、溶媒を抽出溶媒に置換し、未反応物をろ過分離する。抽出溶媒には、エーテル類と飽和脂肪炭化水素又は芳香族炭化水素との混合溶媒が用いられる。好ましくは、THFとトルエンの混合溶媒が用いられる。そして、減圧下、60~200℃でろ液を留去して、溶媒と付加しているエーテルを除去することにより、Eu[C5(CH3)4R]2の粗製物が得られる。
なお、上記2つのいずれの合成方法においても、ろ液の留去が完全でないと、エーテル付加物からエーテルが完全に脱離しない点に注意を要する。
Eu[C5(CH3)4(C2H5)]2の融点は122.4℃、Eu[C5(CH3)4(n-C3H7)]2の融点は49.1℃、Eu[C5(CH3)4(n-C4H9)]2の融点は31.7℃、Eu[C5(CH3)4(n-C5H11)]2は室温で高粘性の液体である。蒸留装置の閉塞を防ぐため、留分を冷却、回収する部位は、55~130℃程度であることが好ましい。また、初留分の約3%は、溶媒や付加したエーテルが含まれているため、除去することが好ましい。さらに、わずかに付加しているエーテルを完全に除くため、蒸留は2回以上繰り返すことが好ましい。
膜形成の際のEu[C5(CH3)4R]2の供給方法としては、Eu[C5(CH3)4R]2を100~180℃に加熱して流動性のある液体とし、キャリアガスをバブリングすることにより気化させる方法や、Eu[C5(CH3)4R]2を不活性な炭化水素溶媒に溶解して、液体マスフローメーターで供給し、170~350℃の気化器で全量気化させる方法を用いることができる。
このときに用いられる溶媒としては、溶解度が比較的高い芳香族炭化水素が好ましく、特に、テトラリン等の高沸点溶媒が好ましい。
また、Eu[C5(CH3)4R]2の蒸気と、アンモニアやヒドラジン等の窒化物を窒化剤として用いれば、CVD法やALD法によって窒化ユーロピウム膜を形成することができる。
また、Eu[C5(CH3)4R]2の蒸気と、硫化水素等の硫化物を硫化剤として用いれば、CVD法やALD法によって硫化ユーロピウム膜を形成することができる。
[実施例1]Eu[C5(CH3)4(n-C3H7)]2の合成(液体アンモニア法)
1Lの4ツ口フラスコに脱水トルエン400ml、金属Eu 20.7g(0.136mol)、C5(CH3)4(n-C3H7)H 53.6g(0.33mol)を入れ、-70℃以下に冷却した。これに、アンモニアガス約150gをゆっくり吹き込みながら3時間撹拌した。外部からの冷却を止め、反応液中の液体アンモニアの気化熱による冷却を行いながら撹拌し、室温まで徐々に自然昇温させた。金属Euが完全に反応したことを確認した後、THF250mlを加え、オイルバスを50℃に設定して3時間撹拌した。
一晩放置後、上澄みを1μmのフッ素樹脂フィルターでろ別し、ろ液を110℃で減圧留去し、59.2gの固形分を得た。
得られた固形分を単蒸留装置に仕込み、160~210℃、0.01~0.1torrで真空蒸留を2回行ったところ、濃赤色の留分が得られ、室温で固化した。収量44.3g(0.0926mol)、収率68%(金属Eu基準)であった。
(1)組成分析
湿式分解して得られた液のICP発光分光分析の結果、Eu含有量は31.2%であった(理論値31.8%)。
(2)EI-MS分析
JMS-T100GC型質量分析計(日本電子製)にて、測定条件を、イオン化法:EI(+)、イオン源温度:230℃、イオン化電流:150μA、イオン化電圧:70V、加速電圧:7kV、測定範囲:m/z35~800として分析を行った。
図1に、このEI-MSスペクトルを示す。図1に示したように、EI-MSにおいて、分子イオン(m/z479.20)が検出されたことから、分析試料はEu[C5(CH3)4(n-C3H7)]2であると同定された。
(3)TG-DTA
測定条件を、試料重量:18.75mg、雰囲気Ar1気圧、昇温速度10.0℃/minとして、TG-DTA測定を行った。
図2に、このTG-DTA測定結果を示す。図2に示したように、49.1℃において、重量変化を伴わない吸熱ピークが確認された。これは、Eu[C5(CH3)4(n-C3H7)]2の溶融によるものである。
また、350℃までに98.3%が蒸発していることが確認された。このことから、Eu[C5(CH3)4(n-C3H7)]2は、350℃以下においては分オーダーの短時間での熱劣化はせず、ALD法やCVD法の原料に求められる熱安定性を有していると言える。
(4)蒸気圧
気体飽和法による測定の結果、0.1torr/161℃であった。
ジムロート付き2Lフラスコに、THF 800ml、NaH 15.5g(0.646mol)、C5(CH3)4(n-C3H7)H 101g(0.615mol)を入れ、60時間反応させた後、未反応分をろ過して分離した。ろ液に無水のEuI2 92.6g(0.228mol)を加え、オイルバスを40℃に設定して31時間加温撹拌した。
次に、THFを留去した後、トルエン1000mlとTHF 160mlを加え、加熱還流させた。反応液を室温まで冷却し、ろ過した後、110℃で減圧留去し、62.1gの固形分を得た。
得られた固形分を単蒸留装置に仕込み、160~200℃、0.01~0.1torrで真空蒸留を2回行ったところ、濃赤色の留分が得られ、室温で固化した。収量22.1g(0.0462mol)、収率28%(金属Eu基準)であった。
蒸留して得られたEu[C5(CH3)4(n-C3H7)]2について、実施例1と同様に組成分析を行ったところ、Eu金属含有量は、31.3%であった(理論値31.8%)。
実施例1で得られたEu[C5(CH3)4(n-C3H7)]2 30gを充填したシリンダを170℃に加熱しながら、Arガス100sccmでバブリングし(Aパルス)、一方、水を充填したシリンダを20℃に加熱しながら、Arガス50sccmでバブリングし(Bパルス)、パージガスとしてAr200sccmを流し、各パルス導入1秒、パージ3秒で、ALD操作を行った。
圧力約5torrのALDチャンバ内に、基板温度300℃のSi基板を置き、(Aパルス導入→パージ→Bパルス導入→パージ)の工程を100サイクル行い、厚さ10nmのEu2O3膜を得た。
なお、Eu[C5(CH3)4(n-C3H7)]2の充填量を5gとして、同様にして、成膜を行った場合においても、充填量30gの場合との成膜速度の違いはなく、使用状況によって供給量に変化がないことが確認された。
C5(CH3)4(n-C3H7)Hの代わりに、C5(CH3)4(C2H5)Hを用いる以外は、実施例1と同様の方法で合成を行ったところ、収率53.5%でEu[C5(CH3)4(C2H5)]2が得られた。大気中の水分や酸素に触れると直ちに分解する固体であった。
蒸留操作中において観察された蒸気圧は0.02torr/152℃であった。
図3に、TG-DTA測定結果を示す。図3に示したように、122.4℃に融点が観測された。また、350℃までに熱分解せず、98.13%が蒸発していることが確認された。
水や酸素等の酸化剤との反応性、蒸気圧、融点及び熱安定性等の分析結果から、本化合物がCVD法やALD法によるユーロピウム含有薄膜形成用前駆体として好適な性質を有していることが認められた。
C5(CH3)4(n-C3H7)Hの代わりに、C5(CH3)4(n-C4H9)Hを用いる以外は、実施例1と同様の方法で合成を行ったところ、収率35.4%でEu[C5(CH3)4(n-C4H9)]2が得られた。大気中の水分や酸素に触れると直ちに分解する固体であった。
蒸留操作中において観察された蒸気圧は0.25torr/172℃であった。
図4に、TG-DTA測定結果を示す。図4に示したように、31.7℃に融点が観測された。また、350℃までに熱分解せず、97.51%が蒸発していることが確認された。
水や酸素等の酸化剤との反応性、蒸気圧、融点及び熱安定性等の分析結果から、本化合物がCVD法やALD法によるユーロピウム含有薄膜形成用前駆体として好適な性質を有していることが認められた。
C5(CH3)4(n-C3H7)Hの代わりに、C5(CH3)4(n-C5H11)Hを用いる以外は、実施例1と同様の方法で合成を行ったところ、収率38.6%でEu[C5(CH3)4(n-C5H11)]2が得られた。室温で高粘性の液体であり、大気中の水分や酸素に触れると直ちに分解した。
蒸留操作中において観察された蒸気圧は0.01torr/155℃であった。
図5に、TG-DTA測定結果を示す。図5に示したように、400℃までに熱分解せず、96.82%が蒸発していることが確認された。
水や酸素等の酸化剤との反応性、蒸気圧、融点及び熱安定性等の分析結果から、本化合物がCVD法又はALD法によるユーロピウム含有薄膜形成用前駆体として好適な性質を有していることが認められた。
300mlの4ツ口フラスコに脱水トルエン100ml、金属Eu 6.4g(0.042mol)、C5(CH3)5H 22.8g(0.167mol)を入れ、-70℃以下に冷却した。これに、アンモニアガス約50gをゆっくり吹き込みながら3時間撹拌した。外部からの冷却を止め、反応液中の液体アンモニアの気化熱による冷却を行いながら撹拌し、室温まで徐々に自然昇温させた。金属Euが完全に反応したことを確認した後、THF100mlを加え、オイルバスを50℃に設定して3時間撹拌した。
一晩放置後、上澄みを1μmのフッ素樹脂フィルターでろ別し、ろ液を110℃で減圧留去したところ、褐色の固形分を得た。
得られた固形分を昇華装置に入れ、240℃、0.01~0.1torrで昇華精製を2回行ったところ、濃紫色の固体が得られた。収量8.5g、収率48%であった。
図6に、TG-DTA測定結果を示す。図6に示したように、211.2℃に融点が観測された。この結果から分かるように、本化合物はバブリングでの供給が困難であり、また蒸留による精製も困難である。
Claims (5)
- Eu[C5(CH3)4R]2(式中、Rは炭素数2以上のアルキル基)で表されるビス(テトラメチルモノアルキルシクロペンタジエニル)ユーロピウム。
- 前記Rが炭素数2~5のアルキル基であることを特徴とする請求項1記載のビス(テトラメチルモノアルキルシクロペンタジエニル)ユーロピウム。
- 前記Rがエチル基、n-プロピル基、n-ブチル基及びn-ペンチル基のうちのいずれかであることを特徴とする請求項1又は2に記載のビス(テトラメチルモノアルキルシクロペンタジエニル)ユーロピウム。
- 請求項1~3のいずれか1項に記載されたビス(テトラメチルモノアルキルシクロペンタジエニル)ユーロピウムであることを特徴とする化学的気相法又は原子層堆積法によるユーロピウム含有薄膜形成用前駆体。
- 請求項4に記載されたユーロピウム含有薄膜形成用前駆体を用いることを特徴とするユーロピウム含有薄膜の形成方法。
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US14/007,474 US8747965B2 (en) | 2011-03-29 | 2012-02-23 | Precursor for formation of europium-containing thin film, and method for forming europium-containing thin film |
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JP2019134154A (ja) * | 2018-01-26 | 2019-08-08 | レール・リキード−ソシエテ・アノニム・プール・レテュード・エ・レクスプロワタシオン・デ・プロセデ・ジョルジュ・クロード | ランタノイド化合物、ランタノイド含有薄膜、および該ランタノイド化合物を用いたランタノイド含有薄膜の成膜方法 |
WO2020116182A1 (ja) * | 2018-12-06 | 2020-06-11 | 株式会社高純度化学研究所 | ビス(アルキルテトラメチルシクロペンタジエニル)亜鉛、化学蒸着用原料、および亜鉛を含有する薄膜の製造方法 |
WO2021029215A1 (ja) * | 2019-08-09 | 2021-02-18 | 株式会社高純度化学研究所 | ビス(エチルシクロペンタジエニル)スズ、化学蒸着用原料、スズを含有する薄膜の製造方法、およびスズ酸化物薄膜の製造方法 |
JP2021025121A (ja) * | 2019-08-09 | 2021-02-22 | 株式会社高純度化学研究所 | 化学蒸着用原料、スズを含有する薄膜の製造方法、およびスズ酸化物薄膜の製造方法 |
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US11784041B2 (en) * | 2022-02-08 | 2023-10-10 | L'Air Liquide, Sociéte Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude | Preparation of lanthanide-containing precursors and deposition of lanthanide-containing films |
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JP2019134154A (ja) * | 2018-01-26 | 2019-08-08 | レール・リキード−ソシエテ・アノニム・プール・レテュード・エ・レクスプロワタシオン・デ・プロセデ・ジョルジュ・クロード | ランタノイド化合物、ランタノイド含有薄膜、および該ランタノイド化合物を用いたランタノイド含有薄膜の成膜方法 |
JP7235466B2 (ja) | 2018-01-26 | 2023-03-08 | レール・リキード-ソシエテ・アノニム・プール・レテュード・エ・レクスプロワタシオン・デ・プロセデ・ジョルジュ・クロード | ランタノイド化合物、ランタノイド含有薄膜、および該ランタノイド化合物を用いたランタノイド含有薄膜の成膜方法 |
WO2020116182A1 (ja) * | 2018-12-06 | 2020-06-11 | 株式会社高純度化学研究所 | ビス(アルキルテトラメチルシクロペンタジエニル)亜鉛、化学蒸着用原料、および亜鉛を含有する薄膜の製造方法 |
JP2020090712A (ja) * | 2018-12-06 | 2020-06-11 | 株式会社高純度化学研究所 | ビス(アルキルテトラメチルシクロペンタジエニル)亜鉛、化学蒸着用原料、および亜鉛を含有する薄膜の製造方法 |
JP7114072B2 (ja) | 2018-12-06 | 2022-08-08 | 株式会社高純度化学研究所 | ビス(アルキルテトラメチルシクロペンタジエニル)亜鉛、化学蒸着用原料、および亜鉛を含有する薄膜の製造方法 |
WO2021029215A1 (ja) * | 2019-08-09 | 2021-02-18 | 株式会社高純度化学研究所 | ビス(エチルシクロペンタジエニル)スズ、化学蒸着用原料、スズを含有する薄膜の製造方法、およびスズ酸化物薄膜の製造方法 |
JP2021025121A (ja) * | 2019-08-09 | 2021-02-22 | 株式会社高純度化学研究所 | 化学蒸着用原料、スズを含有する薄膜の製造方法、およびスズ酸化物薄膜の製造方法 |
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