TW201716417A - Method of producing aluminum oxide film, raw material for producing aluminum oxide film, and aluminum compound - Google Patents
Method of producing aluminum oxide film, raw material for producing aluminum oxide film, and aluminum compound Download PDFInfo
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- TW201716417A TW201716417A TW105126476A TW105126476A TW201716417A TW 201716417 A TW201716417 A TW 201716417A TW 105126476 A TW105126476 A TW 105126476A TW 105126476 A TW105126476 A TW 105126476A TW 201716417 A TW201716417 A TW 201716417A
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- oxide film
- aluminum oxide
- aluminum
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 title claims abstract description 108
- -1 aluminum compound Chemical class 0.000 title claims abstract description 103
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 76
- 238000000034 method Methods 0.000 title claims abstract description 42
- 239000002994 raw material Substances 0.000 title claims description 20
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 31
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 23
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims abstract description 16
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims abstract description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 13
- 230000001590 oxidative effect Effects 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims description 41
- 238000004519 manufacturing process Methods 0.000 claims description 41
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 16
- 239000000126 substance Substances 0.000 claims description 16
- 238000000231 atomic layer deposition Methods 0.000 claims description 9
- 238000005229 chemical vapour deposition Methods 0.000 claims description 7
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 239000010408 film Substances 0.000 description 151
- 239000000758 substrate Substances 0.000 description 39
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 38
- 239000007789 gas Substances 0.000 description 28
- 239000000203 mixture Substances 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 20
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 15
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 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 13
- 238000004458 analytical method Methods 0.000 description 12
- 229940125782 compound 2 Drugs 0.000 description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 11
- IDVWLLCLTVBSCS-UHFFFAOYSA-N n,n'-ditert-butylmethanediimine Chemical compound CC(C)(C)N=C=NC(C)(C)C IDVWLLCLTVBSCS-UHFFFAOYSA-N 0.000 description 11
- 229910052786 argon Inorganic materials 0.000 description 9
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 9
- 239000012295 chemical reaction liquid Substances 0.000 description 8
- 239000012141 concentrate Substances 0.000 description 8
- 230000008016 vaporization Effects 0.000 description 8
- 239000006200 vaporizer Substances 0.000 description 8
- ORVACBDINATSAR-UHFFFAOYSA-N dimethylaluminum Chemical compound C[Al]C ORVACBDINATSAR-UHFFFAOYSA-N 0.000 description 7
- 230000000704 physical effect Effects 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 238000009834 vaporization Methods 0.000 description 7
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- CQYBWJYIKCZXCN-UHFFFAOYSA-N diethylaluminum Chemical compound CC[Al]CC CQYBWJYIKCZXCN-UHFFFAOYSA-N 0.000 description 5
- 238000004821 distillation Methods 0.000 description 5
- 238000002955 isolation Methods 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 4
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 4
- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethylcyclohexane Chemical compound CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 description 4
- 238000002309 gasification Methods 0.000 description 4
- 150000004820 halides Chemical class 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 3
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- CAVCGVPGBKGDTG-UHFFFAOYSA-N alumanylidynemethyl(alumanylidynemethylalumanylidenemethylidene)alumane Chemical compound [Al]#C[Al]=C=[Al]C#[Al] CAVCGVPGBKGDTG-UHFFFAOYSA-N 0.000 description 2
- 239000003708 ampul Substances 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- JGHYBJVUQGTEEB-UHFFFAOYSA-M dimethylalumanylium;chloride Chemical compound C[Al](C)Cl JGHYBJVUQGTEEB-UHFFFAOYSA-M 0.000 description 2
- BLHLJVCOVBYQQS-UHFFFAOYSA-N ethyllithium Chemical compound [Li]CC BLHLJVCOVBYQQS-UHFFFAOYSA-N 0.000 description 2
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 2
- DVSDBMFJEQPWNO-UHFFFAOYSA-N methyllithium Chemical compound C[Li] DVSDBMFJEQPWNO-UHFFFAOYSA-N 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- VZXTWGWHSMCWGA-UHFFFAOYSA-N 1,3,5-triazine-2,4-diamine Chemical compound NC1=NC=NC(N)=N1 VZXTWGWHSMCWGA-UHFFFAOYSA-N 0.000 description 1
- BDNKZNFMNDZQMI-UHFFFAOYSA-N 1,3-diisopropylcarbodiimide Chemical compound CC(C)N=C=NC(C)C BDNKZNFMNDZQMI-UHFFFAOYSA-N 0.000 description 1
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 1
- MVECFARLYQAUNR-UHFFFAOYSA-N CCCC[Mg]CC Chemical compound CCCC[Mg]CC MVECFARLYQAUNR-UHFFFAOYSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- JJSGABFIILQOEY-UHFFFAOYSA-M diethylalumanylium;bromide Chemical compound CC[Al](Br)CC JJSGABFIILQOEY-UHFFFAOYSA-M 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- BGRWYRAHAFMIBJ-UHFFFAOYSA-N diisopropylcarbodiimide Natural products CC(C)NC(=O)NC(C)C BGRWYRAHAFMIBJ-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- ZGMHEOLLTWPGQX-UHFFFAOYSA-M dimethylalumanylium;bromide Chemical compound C[Al](C)Br ZGMHEOLLTWPGQX-UHFFFAOYSA-M 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 description 1
- KJJBSBKRXUVBMX-UHFFFAOYSA-N magnesium;butane Chemical compound [Mg+2].CCC[CH2-].CCC[CH2-] KJJBSBKRXUVBMX-UHFFFAOYSA-N 0.000 description 1
- DLPASUVGCQPFFO-UHFFFAOYSA-N magnesium;ethane Chemical compound [Mg+2].[CH2-]C.[CH2-]C DLPASUVGCQPFFO-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 239000008400 supply water Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-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
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/06—Aluminium 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
- C23C16/40—Oxides
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Formation Of Insulating Films (AREA)
- Chemical Vapour Deposition (AREA)
Abstract
Description
本揭示關於氧化鋁膜之製造方法、氧化鋁膜之製造原料、及鋁化合物。The present disclosure relates to a method for producing an aluminum oxide film, a raw material for producing an aluminum oxide film, and an aluminum compound.
氧化鋁膜作為閘極絕緣膜等係有用，在半導體領域中廣泛應用展開。因此，人們研究用於製造氧化鋁膜的鋁化合物(氧化鋁膜之製造原料)(例如，參照專利文獻1～4)。The aluminum oxide film is useful as a gate insulating film or the like, and is widely used in the field of semiconductors. Therefore, an aluminum compound (a raw material for producing an aluminum oxide film) for producing an aluminum oxide film has been studied (for example, refer to Patent Documents 1 to 4).
另一方面，非專利文獻1中揭示了作為聚合觸媒的(二第三丁基(甲基)脒基(amidinato))二甲基鋁。但，並無任何關於物性值及特性的記載。又，非專利文獻2中揭示了(二第三丁基(乙基)脒基)二乙基鋁的合成例。但，並無任何關於特性的記載。 [先前技術文獻] [專利文獻]On the other hand, Non-Patent Document 1 discloses (di-t-butyl(methyl)amidinato)dimethylaluminum as a polymerization catalyst. However, there is no record of physical property values and characteristics. Further, Non-Patent Document 2 discloses a synthesis example of (di-t-butyl(ethyl)fluorenyl)diethylaluminum. However, there is no record of the characteristics. [Prior Technical Literature] [Patent Literature]
專利文獻1：日本特表2006-526705號公報 專利文獻2：日本專利第4716193號公報 專利文獻3：日本特開2007-138296號公報 專利文獻4：韓國登錄專利第10-1221861號公報 [非專利文獻]Patent Document 1: Japanese Patent Publication No. 2006-526705 Patent Document 2: Japanese Patent No. 4,716,193 Patent Document 3: Japanese Patent Laid-Open No. 2007-138296 Patent Document 4: Korean Patent Application No. 10-1221861 [Non-patent literature]
非專利文獻1：J. Phys. Chem. A, 105, 3867-3874(2001) 非專利文獻2：Organometallics, 17, 1595-1601(1998)Non-Patent Document 1: J. Phys. Chem. A, 105, 3867-3874 (2001) Non-Patent Document 2: Organometallics, 17, 1595-1601 (1998)
[發明所欲解決之課題] 尋求一種能穩定地製造氧化鋁膜的新氧化鋁膜之製造方法。[Problems to be Solved by the Invention] A method for producing a novel aluminum oxide film capable of stably producing an aluminum oxide film has been sought.
因此，本揭示於一方面提供一種能穩定地製造厚度之變異減小之氧化鋁膜的氧化鋁膜之製造方法。又，於另一方面提供適合用於該製造方法的製造原料、及鋁化合物。 [解決課題之手段]Accordingly, the present disclosure provides, in one aspect, a method of producing an aluminum oxide film capable of stably producing an aluminum oxide film having a reduced variation in thickness. Further, on the other hand, a raw material for production and an aluminum compound suitable for use in the production method are provided. [Means for solving the problem]
本發明於一方面提供一種氧化鋁膜之製造方法，具有以下步驟：藉由將下式(1)表示之鋁化合物供給至加熱的成膜對象物上，並將鋁化合物氧化而在成膜對象物上形成氧化鋁膜。The present invention provides a method for producing an aluminum oxide film, which comprises the steps of: supplying an aluminum compound represented by the following formula (1) to a heated film formation object, and oxidizing the aluminum compound to form a film formation object An aluminum oxide film is formed on the object.
【化學式1】 [Chemical Formula 1]
上式(1)中，R表示碳原子數1～2之直鏈狀烷基，多個R彼此可相同也可不同。t-Bu表示第三丁基。In the above formula (1), R represents a linear alkyl group having 1 to 2 carbon atoms, and a plurality of R's may be the same or different. t-Bu represents a third butyl group.
上述製造方法可穩定地製造厚度之變異減小之氧化鋁膜。其理由據推斷係由於：上式(1)表示之鋁化合物於加熱下可輕易地分解，同時於加熱下可穩定地以膜狀的形態析出氧化鋁。The above manufacturing method can stably produce an alumina film having a reduced variation in thickness. The reason for this is presumed to be because the aluminum compound represented by the above formula (1) can be easily decomposed under heating, and the alumina can be stably precipitated in a film form under heating.
在幾個實施形態中，上述成膜對象物宜加熱至300～500℃較佳。藉此，可進一步減小氧化鋁膜之厚度之變異。又，可充分減少氧化鋁膜所含之雜質，而製造高品質的氧化鋁膜。In some embodiments, it is preferred that the film formation object is heated to 300 to 500 °C. Thereby, the variation in the thickness of the aluminum oxide film can be further reduced. Further, a high-quality aluminum oxide film can be produced by sufficiently reducing the impurities contained in the aluminum oxide film.
上述鋁化合物亦可包含下式(1-1)表示之化合物。The above aluminum compound may also contain a compound represented by the following formula (1-1).
【化學式2】 [Chemical Formula 2]
上式(1-1)中，R1 及R2 表示彼此不同的烷基。R1 及R2 各自獨立地表示碳原子數1～2之直鏈狀烷基，多個R1 彼此可相同也可不同。t-Bu表示第三丁基。In the above formula (1-1), R 1 and R 2 each represent an alkyl group different from each other. R 1 and R 2 each independently represent a linear alkyl group having 1 to 2 carbon atoms, and a plurality of R 1 's may be the same or different. t-Bu represents a third butyl group.
上式(1-1)表示之鋁化合物，藉由包含甲基，蒸氣壓變高，可減少使其氣化時所需的能量。The aluminum compound represented by the above formula (1-1), by containing a methyl group, has a high vapor pressure, and can reduce the energy required for vaporization.
上述步驟中，宜利用原子層沉積法(Atomic Layer Deposition；以下有時亦稱為「ALD法」。)或化學氣相蒸鍍法(Chemical Vapor Deposition法；以下有時亦稱為「CVD法」。)形成氧化鋁膜較佳。藉此，可形成更加高品質的氧化鋁膜。In the above steps, it is preferable to use an atomic layer deposition method (hereinafter sometimes referred to as "ALD method") or a chemical vapor deposition method (Chemical Vapor Deposition method; hereinafter sometimes referred to as "CVD method") It is preferred to form an aluminum oxide film. Thereby, a higher quality aluminum oxide film can be formed.
本發明於另一方面提供一種包含下式(1)表示之鋁化合物的氧化鋁膜之製造原料。In another aspect, the present invention provides a raw material for producing an aluminum oxide film comprising an aluminum compound represented by the following formula (1).
【化學式3】 [Chemical Formula 3]
上式(1)中，R表示碳原子數1～2之直鏈狀烷基，多個R彼此可相同也可不同。t-Bu表示第三丁基。In the above formula (1), R represents a linear alkyl group having 1 to 2 carbon atoms, and a plurality of R's may be the same or different. t-Bu represents a third butyl group.
只要是將上式(1)表示之鋁化合物用作氧化鋁膜之製造原料的方法，即可穩定地製造厚度之變異減小之氧化鋁膜。其理由據推斷係由於：上述鋁化合物藉由在氧源的存在下加熱可輕易地分解，同時可穩定地以膜狀的形態析出氧化鋁。As long as the aluminum compound represented by the above formula (1) is used as a raw material for producing an aluminum oxide film, an alumina film having a reduced variation in thickness can be stably produced. The reason for this is presumed to be that the aluminum compound can be easily decomposed by heating in the presence of an oxygen source, and alumina can be stably precipitated in a film form.
上述鋁化合物亦可包含下式(1-1)表示之化合物。The above aluminum compound may also contain a compound represented by the following formula (1-1).
【化學式4】 [Chemical Formula 4]
上式(1-1)中，R1 及R2 為彼此不同的烷基。R1 及R2 各自獨立地表示碳原子數1～2之直鏈狀烷基，多個R1 彼此可相同也可不同。t-Bu表示第三丁基。In the above formula (1-1), R 1 and R 2 are alkyl groups different from each other. R 1 and R 2 each independently represent a linear alkyl group having 1 to 2 carbon atoms, and a plurality of R 1 's may be the same or different. t-Bu represents a third butyl group.
上式(1-1)表示之鋁化合物，藉由包含甲基，蒸氣壓變高，可減少使其氣化時所需的能量。The aluminum compound represented by the above formula (1-1), by containing a methyl group, has a high vapor pressure, and can reduce the energy required for vaporization.
本發明於又另一方面提供一種下列式(1-1)表示之鋁化合物。In still another aspect, the present invention provides an aluminum compound represented by the following formula (1-1).
【化學式5】 [Chemical Formula 5]
式(1-1)中，R1 及R2 表示彼此不同的烷基。R1 及R2 各自獨立地表示碳原子數1～2之直鏈狀烷基，多個R1 彼此可相同也可不同。t-Bu表示第三丁基。In the formula (1-1), R 1 and R 2 each represent an alkyl group different from each other. R 1 and R 2 each independently represent a linear alkyl group having 1 to 2 carbon atoms, and a plurality of R 1 's may be the same or different. t-Bu represents a third butyl group.
上述鋁化合物於加熱下可輕易地分解，同時即使於加熱下仍可穩定地以膜狀的形態析出氧化鋁。故，可穩定地製造具有指定厚度的氧化鋁膜。 [發明之效果]The above aluminum compound can be easily decomposed under heating, and at the same time, alumina can be stably precipitated in a film form even under heating. Therefore, an alumina film having a specified thickness can be stably produced. [Effects of the Invention]
本揭示於一方面可提供一種能穩定地製造厚度之變異減小之氧化鋁膜的氧化鋁膜之製造方法。又，於另一方面可提供適合用於該製造方法的製造原料、及鋁化合物。The present invention provides, in one aspect, a method for producing an aluminum oxide film capable of stably producing an aluminum oxide film having a reduced variation in thickness. Further, on the other hand, a raw material for production and an aluminum compound suitable for the production method can be provided.
以下對本發明之一實施形態進行說明。本實施形態之氧化鋁膜之製造方法具有以下步驟：藉由將鋁化合物供給至加熱的成膜對象物上，並將該鋁化合物氧化而在成膜對象物上形成氧化鋁膜。Hereinafter, an embodiment of the present invention will be described. The method for producing an aluminum oxide film according to the present embodiment has a step of forming an aluminum oxide film on a film formation object by supplying an aluminum compound to a heated film formation object and oxidizing the aluminum compound.
氧化鋁膜之製造方法所使用的鋁化合物係下式(1)表示之(二第三丁基(烷基)脒基)二烷基鋁化合物。The aluminum compound used in the method for producing an aluminum oxide film is a (di-t-butyl(alkyl)fluorenyl)dialkylaluminum compound represented by the following formula (1).
【化學式6】 [Chemical Formula 6]
上式(1)中，R表示碳原子數1～2之直鏈狀烷基，多個R可相同也可不同。t-Bu表示第三丁基。式(1)中之R(烷基)，例如，可列舉甲基、乙基。In the above formula (1), R represents a linear alkyl group having 1 to 2 carbon atoms, and a plurality of R's may be the same or different. t-Bu represents a third butyl group. The R (alkyl group) in the formula (1) may, for example, be a methyl group or an ethyl group.
上式(1)表示之(二第三丁基(烷基)脒基)二烷基鋁化合物宜包含下式(1-1)表示之化合物較佳。The (di-tert-butyl(alkyl)fluorenyl)dialkylaluminum compound represented by the above formula (1) preferably contains a compound represented by the following formula (1-1).
【化學式7】 [Chemical Formula 7]
上式(1-1)中，R1 及R2 為彼此不同的烷基。R1 及R2 各自獨立地表示碳原子數1～2之直鏈狀烷基。2個R1 彼此可相同也可不同。但，以降低製造成本、原料取得的容易性的觀點觀之，2個R1 宜相同較佳。t-Bu表示第三丁基。In the above formula (1-1), R 1 and R 2 are alkyl groups different from each other. R 1 and R 2 each independently represent a linear alkyl group having 1 to 2 carbon atoms. The two R 1 's may be the same or different from each other. However, from the viewpoint of reducing the manufacturing cost and the ease of obtaining the raw materials, the two R 1 should preferably be the same. t-Bu represents a third butyl group.
氧化鋁膜之製造方法所使用的鋁化合物的理想具體例，可列舉下式(2)～(5)表示之化合物。A preferred example of the aluminum compound used in the method for producing the aluminum oxide film is a compound represented by the following formulas (2) to (5).
【化學式8】 [Chemical Formula 8]
上式(2)～(5)中之t-Bu表示第三丁基，Me及Et分別表示甲基及乙基。亦即，式(2)表示之化合物係(二第三丁基(甲基)脒基)二甲基鋁，式(3)表示之化合物係(二第三丁基(乙基)脒基)二乙基鋁。式(4)表示之化合物係(二第三丁基(乙基)脒基)二甲基鋁，式(5)表示之化合物係(二第三丁基(甲基)脒基)二乙基鋁。t-Bu in the above formulas (2) to (5) represents a third butyl group, and Me and Et represent a methyl group and an ethyl group, respectively. That is, the compound represented by the formula (2) is (di-t-butyl(methyl)indenyl)dimethylaluminum, and the compound represented by the formula (3) is (di-t-butyl(ethyl)fluorenyl). Diethylaluminum. The compound represented by the formula (4) is (di-t-butyl(ethyl)decyl)dimethylaluminum, and the compound represented by the formula (5) is (di-t-butyl(methyl)indenyl)diethyl. aluminum.
上式(1)、(1-1)、(2)～(5)表示之各鋁化合物，為了在成膜對象物上形成氧化鋁膜可適當地使用。亦即，適於成膜對象物上之氧化鋁膜的形成用途。亦可使用用於形成氧化鋁膜的上式(1)、(1-1)或(2)～(5)表示之鋁化合物。Each of the aluminum compounds represented by the above formulas (1), (1-1), and (2) to (5) can be suitably used in order to form an aluminum oxide film on the film formation object. That is, it is suitable for the formation of an aluminum oxide film on a film formation object. An aluminum compound represented by the above formula (1), (1-1) or (2) to (5) for forming an aluminum oxide film can also be used.
(二第三丁基(烷基)脒基)二烷基鋁化合物，例如，可利用下列方法1或方法2等進行製造。The (di-t-butyl(alkyl)decyl)dialkylaluminum compound can be produced, for example, by the following method 1 or method 2 or the like.
方法1具有以下步驟：第1步驟，係使二第三丁基碳二亞胺與烷基鹼金屬化合物反應，或使二第三丁基碳二亞胺與烷基鹼土類金屬化合物反應，而獲得二第三丁基(烷基)脒之金屬鹽；第2步驟，係使獲得之金屬鹽與二烷基鹵化鋁反應。The method 1 has the following steps: in the first step, the reaction of the di-tert-butylcarbodiimide with the alkyl alkali metal compound or the reaction of the di-tert-butylcarbodiimide with the alkyl alkaline earth metal compound; A metal salt of di-tert-butyl(alkyl)anthracene is obtained; in the second step, the obtained metal salt is reacted with a dialkylaluminum halide.
方法2具有以下步驟：使二第三丁基碳二亞胺與三烷基鋁反應。Process 2 has the step of reacting di-tert-butylcarbodiimide with a trialkylaluminum.
方法1中所使用之金屬化合物，例如，可列舉甲基鋰、乙基鋰、正丁基鋰、第二丁基鋰、第三丁基鋰、二乙基鎂、乙基丁基鎂、及二丁基鎂等。可單獨使用該等中之1種，亦可將2種以上組合使用。上述金屬化合物中，以降低製造成本、原料取得的容易性、提高反應產率的觀點觀之，宜為甲基鋰較佳。The metal compound used in the method 1 may, for example, be methyl lithium, ethyl lithium, n-butyl lithium, second butyl lithium, t-butyl lithium, diethyl magnesium, ethyl butyl magnesium, and Dibutyl magnesium and the like. One type of these may be used alone, or two or more types may be used in combination. Among the above metal compounds, methyl lithium is preferred from the viewpoint of reducing the production cost, the easiness of obtaining raw materials, and improving the reaction yield.
鹼金屬化合物之使用量相對於二第三丁基碳二亞胺1莫耳宜為0.4～1.4莫耳較佳，0.6～1.2莫耳更佳。又，鹼土類金屬化合物之使用量相對於二第三丁基碳二亞胺1莫耳宜為0.2～0.7莫耳較佳，0.3～0.6莫耳更佳。The amount of the alkali metal compound to be used is preferably from 0.4 to 1.4 mol, more preferably from 0.6 to 1.2 mol, based on the di-tert-butylcarbodiimide. Further, the amount of the alkaline earth metal compound to be used is preferably from 0.2 to 0.7 mol, more preferably from 0.3 to 0.6 mol, based on the di-tert-butylcarbodiimide.
方法1中所使用之二烷基鹵化鋁，例如，可列舉二甲基氯化鋁、二甲基溴化鋁、二乙基氯化鋁、及二乙基溴化鋁等。可單獨使用該等中之1種，亦可將2種以上組合使用。上述二烷基鹵化鋁中，以降低製造成本、原料取得的容易性、及提高反應產率的觀點觀之，宜為二乙基氯化鋁較佳。Examples of the dialkyl aluminum halide used in the method 1 include dimethyl aluminum chloride, dimethyl aluminum bromide, diethyl aluminum chloride, and diethyl aluminum bromide. One type of these may be used alone, or two or more types may be used in combination. Among the above dialkylaluminum halides, diethylaluminum chloride is preferred from the viewpoint of reducing the production cost, the easiness of obtaining raw materials, and improving the reaction yield.
二烷基鹵化鋁之使用量相對於二第三丁基(烷基)脒之金屬鹽中之二第三丁基(烷基)脒1莫耳宜為0.1～1.6莫耳較佳，0.5～1.2莫耳更佳。The amount of the dialkyl aluminum halide used is preferably from 0.1 to 1.6 moles, more preferably from 0.1 to 1.6 moles, based on the di-tert-butyl(alkyl)phosphonium metal salt. 1.2 Moore is better.
方法2中所使用之三烷基鋁可列舉三甲基鋁及三乙基鋁等。The trialkyl aluminum used in the method 2 may, for example, be trimethyl aluminum or triethyl aluminum.
三烷基鋁之使用量相對於二第三丁基碳二亞胺1莫耳宜為0.1～1.6莫耳較佳，0.5～1.2莫耳更佳。The amount of the trialkylaluminum to be used is preferably from 0.1 to 1.6 mol, more preferably from 0.5 to 1.2 mol, based on the di-tert-butylcarbodiimide.
方法1及方法2宜分別在有機溶劑中進行較佳。有機溶劑只要是不阻礙反應者即可，並無特別限定。例如，可列舉二***、四氫呋喃、二甲氧基乙烷、二烷等醚類；己烷、庚烷、環己烷、甲基環己烷、乙基環己烷等脂肪族烴類；甲苯、二甲苯等芳香族烴類。該等中，較佳為醚類、脂肪族烴類、醚類與脂肪族烴類之混合溶劑。此外，該等有機溶劑可單獨使用，亦可將2種以上組合使用。The methods 1 and 2 are preferably carried out separately in an organic solvent. The organic solvent is not particularly limited as long as it does not inhibit the reaction. For example, diethyl ether, tetrahydrofuran, dimethoxyethane, and the like may be mentioned. An ether such as an alkane; an aliphatic hydrocarbon such as hexane, heptane, cyclohexane, methylcyclohexane or ethylcyclohexane; or an aromatic hydrocarbon such as toluene or xylene. Among these, a mixed solvent of an ether, an aliphatic hydrocarbon, an ether, and an aliphatic hydrocarbon is preferable. Further, these organic solvents may be used singly or in combination of two or more.
方法1及方法2中之有機溶劑之使用量相對於二烷基鹵化鋁1g或三烷基鋁1g宜為1～100g較佳，5～50g更佳。The amount of the organic solvent used in the method 1 and the method 2 is preferably 1 to 100 g, more preferably 5 to 50 g, per 1 g of the dialkylaluminum halide or 1 g of the trialkylaluminum.
(利用方法1之合成方法) 方法1之反應，例如，可依以下之次序進行。於開始的步驟(第1步驟)中，將二第三丁基碳二亞胺、烷基鹼金屬化合物及有機溶劑混合，邊攪拌邊使其反應而合成二第三丁基(烷基)脒之鹼金屬鹽(二第三丁基(烷基)脒基化合物)。於接下來的步驟(第2步驟)中，加入二烷基鹵化鋁，邊進一步攪拌邊使其反應。第1步驟及第2步驟中之反應溫度宜為-100～100℃較佳，-80～40℃更佳。此時的反應壓力並無特別限制。此外，第1步驟中獲得之二第三丁基(烷基)脒基化合物，在和第2步驟中之二烷基鹵化鋁反應前可暫且單離，亦可直接使用。(Synthesis method using the method 1) The reaction of the method 1 can be carried out, for example, in the following order. In the first step (first step), dibutyl butyl carbodiimide, an alkyl alkali metal compound and an organic solvent are mixed, and reacted with stirring to synthesize di-tert-butyl(alkyl)fluorene. An alkali metal salt (di-t-butyl(alkyl)decyl compound). In the next step (second step), a dialkylaluminum halide is added and reacted with further stirring. The reaction temperature in the first step and the second step is preferably -100 to 100 ° C, more preferably -80 to 40 ° C. The reaction pressure at this time is not particularly limited. Further, the third butyl (alkyl) fluorenyl compound obtained in the first step may be temporarily separated before being reacted with the dialkyl aluminum halide in the second step, or may be used as it is.
(利用方法2之合成方法) 方法2之反應，例如，具有以下步驟：將二第三丁基碳二亞胺、三烷基鋁及有機溶劑混合並使其反應。此時的反應溫度宜為-100～100℃較佳，-80～40℃更佳。此時的反應壓力並無特別限制。(Synthesis Method by Method 2) The reaction of Method 2, for example, has the following steps: mixing and reacting di-tert-butylcarbodiimide, trialkylaluminum, and an organic solvent. The reaction temperature at this time is preferably -100 to 100 ° C, more preferably -80 to 40 ° C. The reaction pressure at this time is not particularly limited.
利用方法1或方法2之反應可獲得(二第三丁基(烷基)脒基)二烷基鋁化合物。反應結束後，(二第三丁基(烷基)脒基)二烷基鋁化合物可利用公知的方法進行單離或精製。公知的方法可列舉萃取、過濾、濃縮、蒸餾、昇華、再結晶及管柱層析等。可單獨使用該等中之1種，亦可將2種以上組合使用。The (di-t-butyl(alkyl)decyl)dialkylaluminum compound can be obtained by the reaction of Process 1 or Process 2. After completion of the reaction, the (di-t-butyl(alkyl)decyl)dialkylaluminum compound can be isolated or purified by a known method. Well-known methods include extraction, filtration, concentration, distillation, sublimation, recrystallization, and column chromatography. One type of these may be used alone, or two or more types may be used in combination.
(二第三丁基(烷基)脒基)二烷基鋁化合物對於大氣中的水分及氧大多不穩定。因此，宜在無水條件下或鈍性氣體條件下進行方法1或方法2之各步驟、及視需要之反應液的後處理等較佳。The (di-t-butyl(alkyl)decyl)dialkylaluminum compound is mostly unstable to moisture and oxygen in the atmosphere. Therefore, it is preferred to carry out the steps of the method 1 or the method 2, and optionally the post-treatment of the reaction liquid under anhydrous conditions or under a passive gas condition.
(二第三丁基(烷基)脒基)二烷基鋁化合物可適當用作用於製造氧化鋁膜的製造原料(製造用原料)。用於製造氧化鋁膜的製造原料(製造用原料)宜僅由(二第三丁基(烷基)脒基)二烷基鋁化合物構成較佳。但，上述製造原料(製造用原料)，在不會對所形成之氧化鋁膜的品質造成大的影響的範圍內，亦可含少量(二第三丁基(烷基)脒基)二烷基鋁化合物以外的雜質(鋁化合物等)。The (di-t-butyl(alkyl)decyl)dialkylaluminum compound can be suitably used as a raw material for production (a raw material for production) for producing an aluminum oxide film. The raw material for production (the raw material for production) for producing an aluminum oxide film is preferably composed of only a (di-t-butyl(alkyl)decyl)dialkylaluminum compound. However, the above-mentioned raw material for production (raw material for production) may contain a small amount (di-t-butyl(alkyl)decyl)-dioxe in a range which does not greatly affect the quality of the formed aluminum oxide film. Impurities other than the base aluminum compound (aluminum compound, etc.).
於成膜對象物上形成氧化鋁膜的方法，例如，可列舉化學氣相蒸鍍法(CVD法)及原子層沉積法(ALD法)。該等中，考量容易控制膜厚、薄膜成膜容易的方面，宜使用ALD法更佳。ALD法的情況下，於成膜對象物上形成氧化鋁膜的步驟，依例如以下之次序進行。A method of forming an aluminum oxide film on a film formation object includes, for example, a chemical vapor deposition method (CVD method) and an atomic layer deposition method (ALD method). Among these, it is preferable to use the ALD method in consideration of the fact that it is easy to control the film thickness and the film formation is easy. In the case of the ALD method, the step of forming an aluminum oxide film on the object to be formed is carried out in the following order, for example.
於常壓或減壓下，將包含(二第三丁基(烷基)脒基)二烷基鋁化合物之氣體、及反應性氣體供給至加熱的成膜對象物上。反應性氣體係具有氧作為構成元素。例如，可列舉氧氣、臭氧等氧化性氣體；水；甲醇、乙醇、正丙醇、異丙醇、正丁醇等醇類。藉由上述反應性氣體將(二第三丁基(烷基)脒基)二烷基鋁化合物予以氧化。藉此，氧化鋁蒸鍍於成膜對象物上，並形成氧化鋁膜。The gas containing the (di-t-butyl(alkyl)fluorenyl)dialkylaluminum compound and the reactive gas are supplied to the heated film formation object under normal pressure or reduced pressure. The reactive gas system has oxygen as a constituent element. For example, an oxidizing gas such as oxygen or ozone; water; an alcohol such as methanol, ethanol, n-propanol, isopropanol or n-butanol may be mentioned. The (di-t-butyl(alkyl)decyl)dialkylaluminum compound is oxidized by the above reactive gas. Thereby, alumina is vapor-deposited on the object to be formed, and an aluminum oxide film is formed.
包含(二第三丁基(烷基)脒基)二烷基鋁化合物之氣體，可為氣體狀之(二第三丁基(烷基)脒基)二烷基鋁化合物經鈍性氣體等稀釋而得者。又，氣體所含之(二第三丁基(烷基)脒基)二烷基鋁化合物亦可為霧狀(液滴狀)。a gas containing a (di-t-butyl(alkyl)fluorenyl)dialkylaluminum compound, which may be a gaseous (di-t-butyl(alkyl)decyl)dialkylaluminum compound, such as a passive gas Diluted to get. Further, the (di-t-butyl(alkyl)decyl)dialkylaluminum compound contained in the gas may be in the form of a mist (droplet shape).
可利用電漿CVD法替代ALD法進行於成膜對象物上形成氧化鋁膜的步驟。該種情況下，可將同樣的原料供給至成膜對象物上，而在成膜對象物上形成氧化鋁膜。The step of forming an aluminum oxide film on the film formation object by the plasma CVD method instead of the ALD method can be employed. In this case, the same raw material can be supplied to the film formation object, and an aluminum oxide film can be formed on the film formation object.
CVD法的情況下，為了形成薄膜(氧化鋁膜)需使(二第三丁基(烷基)脒基)二烷基鋁化合物氣化。使(二第三丁基(烷基)脒基)二烷基鋁化合物氣化的方法，例如，可列舉如下的方法。In the case of the CVD method, in order to form a thin film (aluminum oxide film), a (di-t-butyl(alkyl)fluorenyl)dialkylaluminum compound is vaporized. A method of vaporizing the (di-t-butyl(alkyl)decyl)dialkylaluminum compound, for example, the following method can be mentioned.
亦即，可列舉將(二第三丁基(烷基)脒基)二烷基鋁化合物填充或輸送至氣化室而使其氣化的方法。作為另外的方法，可列舉以下的方法：將(二第三丁基(烷基)脒基)二烷基鋁化合物用適當的溶劑予以稀釋而製備溶液，將該溶液利用液體輸送用泵浦導入至氣化室而使其氣化(溶液法)。That is, a method of filling or transporting a (di-t-butyl(alkyl)fluorenyl)dialkylaluminum compound into a gasification chamber to vaporize it may be mentioned. As another method, a method in which a (di-t-butyl(alkyl)fluorenyl)dialkylaluminum compound is diluted with a suitable solvent to prepare a solution, and the solution is introduced by a pump for liquid transportation It is vaporized to the gasification chamber (solution method).
此處所使用之溶劑可例示己烷、環己烷、甲基環己烷、乙基環己烷、庚烷、辛烷等脂肪族烴類；甲苯、乙苯、二甲苯等芳香族烴類；乙二醇二甲醚、二乙二醇二甲醚、三乙二醇二甲醚、二烷、四氫呋喃等醚類等。可單獨使用該等中之1種，亦可將2種以上組合使用。The solvent to be used herein may, for example, be an aliphatic hydrocarbon such as hexane, cyclohexane, methylcyclohexane, ethylcyclohexane, heptane or octane; or an aromatic hydrocarbon such as toluene, ethylbenzene or xylene; Ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, two An ether such as an alkane or tetrahydrofuran. One type of these may be used alone, or two or more types may be used in combination.
使用(二第三丁基(烷基)脒基)二烷基鋁化合物並將氧化鋁予以蒸鍍而形成氧化鋁膜時反應系統內的壓力宜為1Pa～200kPa較佳，10Pa～110kPa更佳。When the (di-t-butyl(alkyl)decyl)dialkylaluminum compound is used and the alumina is vapor-deposited to form an aluminum oxide film, the pressure in the reaction system is preferably from 1 Pa to 200 kPa, more preferably from 10 Pa to 110 kPa. .
使用(二第三丁基(烷基)脒基)二烷基鋁化合物形成氧化鋁膜時成膜對象物的溫度宜為200～600℃較佳，300～500℃更佳。藉此，可進一步減小氧化鋁膜之厚度之變異。又，可充分減少氧化鋁膜所含之雜質，而製造高品質的氧化鋁膜。進一步，若為300～500℃的話，即使成膜對象物上之溫度多少有些變異，亦可抑制膜厚的變化。故，可輕易地製造膜厚均勻性優異的氧化鋁膜。When the aluminum oxide film is formed using the (di-t-butyl(alkyl)fluorenyl)dialkylaluminum compound, the temperature of the object to be film-formed is preferably 200 to 600 ° C, more preferably 300 to 500 ° C. Thereby, the variation in the thickness of the aluminum oxide film can be further reduced. Further, a high-quality aluminum oxide film can be produced by sufficiently reducing the impurities contained in the aluminum oxide film. Further, when it is 300 to 500 ° C, even if the temperature on the object to be filmed is somewhat changed, the change in film thickness can be suppressed. Therefore, an aluminum oxide film excellent in film thickness uniformity can be easily produced.
使(二第三丁基(烷基)脒基)二烷基鋁化合物氣化時的溫度宜為30～250℃較佳，60～200℃更佳。形成氧化鋁膜時，成為氧源(例如，氧化性氣體、水蒸氣或醇蒸氣、或該等的混合氣體)之反應性氣體相對於全部供給氣體量[反應性氣體＋包含(二第三丁基(烷基)脒基)二烷基鋁化合物之氣體]的含有比例宜為3～99容量%較佳，5～98容量%更佳。The temperature at which the (di-tert-butyl(alkyl)decyl)dialkylaluminum compound is vaporized is preferably from 30 to 250 ° C, more preferably from 60 to 200 ° C. When an aluminum oxide film is formed, a reactive gas which is an oxygen source (for example, an oxidizing gas, water vapor, or alcohol vapor, or a mixed gas thereof) is supplied with respect to the total amount of gas supplied [reactive gas + inclusion (second third) The content of the gas of the (alkyl)fluorenyl)dialkylaluminum compound is preferably from 3 to 99% by volume, more preferably from 5 to 98% by volume.
本實施形態之氧化鋁膜，係藉由將鋁化合物供給至加熱的成膜對象物上，並將該鋁化合物氧化，而形成於成膜對象物上。氧化鋁膜，例如，具有1～100nm，較佳為5～50nm之厚度。The aluminum oxide film of the present embodiment is formed on a film formation target by supplying an aluminum compound to a heated film formation object and oxidizing the aluminum compound. The aluminum oxide film has, for example, a thickness of from 1 to 100 nm, preferably from 5 to 50 nm.
氧化鋁膜可充分減少雜質濃度而製成良好的品質。氧化鋁膜中之氧化鋁的含量例如為95質量%以上，98質量%以上較佳，99質量%以上更佳。如此高純度且薄厚度的高品質氧化鋁膜在半導體領域中係有用。氧化鋁膜可為僅由氧化鋁構成者，亦可為僅由氧化鋁與碳化鋁構成者。本說明書中，氧化鋁之含量為90質量%以上者稱為「氧化鋁膜」。氧化鋁膜之厚度變異例如為未達10nm。此外，氧化鋁膜之厚度之變異係指在任意選擇的地方測得的膜厚之差異(最大值-最小值)。The aluminum oxide film can sufficiently reduce the impurity concentration to produce a good quality. The content of the alumina in the alumina film is, for example, 95% by mass or more, preferably 98% by mass or more, more preferably 99% by mass or more. Such a high-purity and thin-thickness high-quality aluminum oxide film is useful in the field of semiconductors. The aluminum oxide film may be composed only of alumina, or may be composed only of aluminum oxide and aluminum carbide. In the present specification, the content of alumina is 90% by mass or more, which is referred to as "aluminum oxide film". The thickness variation of the aluminum oxide film is, for example, less than 10 nm. Further, the variation in the thickness of the aluminum oxide film means the difference (maximum-minimum value) of the film thickness measured at an arbitrary place.
成膜對象物可列舉包含無機氧化物的基板。藉由在如此之基板之上形成氧化鋁膜，可獲得具有基板與在基板之上之氧化鋁膜的疊層體。The substrate to be coated includes a substrate containing an inorganic oxide. By forming an aluminum oxide film on such a substrate, a laminate having a substrate and an aluminum oxide film on the substrate can be obtained.
以上，針對本發明之實施形態進行了說明，但本發明並不限定於上述實施形態。 [實施例]Although the embodiments of the present invention have been described above, the present invention is not limited to the above embodiments. [Examples]
參照實施例及比較例對本發明之內容進行更詳細地說明，但本發明並不限定於下列實施例。The contents of the present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to the following examples.
[實施例1][(二第三丁基(甲基)脒基)二甲基鋁之合成] 於配備有攪拌裝置、溫度計及滴加漏斗的內容積50ml之燒瓶中，加入三甲基鋁1.26g(17.5mmol)、及己烷20mL並冷卻。於使燒瓶內溫度成為0～6℃之狀態在此緩慢滴加二第三丁基碳二亞胺2.73g(17.5mmol)。滴加結束後，於室溫(25℃)下攪拌15小時。反應結束後，將該反應液濃縮，並將濃縮物進行減壓蒸餾(油浴的溫度：70℃、燒瓶內的壓力：133.3Pa)，獲得白色固體之(二第三丁基(甲基)脒基)二甲基鋁3.44g(單離產率：87%)。[Example 1] Synthesis of [(di-t-butyl(methyl)decyl)dimethylaluminum] In a 50 ml flask equipped with a stirring device, a thermometer, and a dropping funnel, trimethylaluminum was added. 1.26 g (17.5 mmol) and 20 mL of hexane were cooled. 2.73 g (17.5 mmol) of di-tert-butylcarbodiimide was slowly added dropwise to the temperature in the flask at 0 to 6 °C. After completion of the dropwise addition, the mixture was stirred at room temperature (25 ° C) for 15 hours. After completion of the reaction, the reaction liquid was concentrated, and the concentrate was subjected to distillation under reduced pressure (temperature of oil bath: 70 ° C, pressure in a flask: 133.3 Pa) to obtain a white solid (di-tert-butyl (methyl)) Mercapto) dimethylaluminum 3.44 g (isolation yield: 87%).
(二第三丁基(甲基)脒基)二甲基鋁係上式(1)之R為甲基的化合物(上式(2)之化合物)。獲得之(二第三丁基(甲基)脒基)二甲基鋁的物性值如下。(Di-t-butyl(methyl)indenyl)dimethylaluminum is a compound of the above formula (1) wherein R is a methyl group (a compound of the above formula (2)). The physical property values of the obtained (di-t-butyl(methyl)decyl)dimethylaluminum are as follows.
1 H-NMR(C6 D6 ,δ(ppm))；-0.14(6H,s),1.05(18H,s),3.14(3H,s) 1 H-NMR (C 6 D 6 , δ (ppm)); -0.14 (6H, s), 1.05 (18H, s), 3.14 (3H, s)
[實施例2][(二第三丁基(乙基)脒基)二乙基鋁之合成] 於配備有攪拌裝置、溫度計及滴加漏斗的內容積50ml之燒瓶中，加入三乙基鋁2.00g(17.5mmol)、及己烷20mL並冷卻。於使燒瓶內溫度成為0～6℃之狀態在此緩慢滴加二第三丁基碳二亞胺2.73g(17.5mmol)。滴加結束後，於室溫下攪拌15小時。反應結束後，將該反應液濃縮，並將濃縮物進行減壓蒸餾(油浴溫度：80℃、燒瓶內的壓力：133.3Pa)，獲得無色透明液體之(二第三丁基(乙基)脒基)二乙基鋁4.43g(單離產率：94%)。[Example 2] Synthesis of [(di-t-butyl(ethyl)decyl)diethylaluminum] In a 50 ml flask equipped with a stirring device, a thermometer, and a dropping funnel, triethylaluminum was added. 2.00 g (17.5 mmol) and 20 mL of hexane were cooled. 2.73 g (17.5 mmol) of di-tert-butylcarbodiimide was slowly added dropwise to the temperature in the flask at 0 to 6 °C. After the completion of the dropwise addition, the mixture was stirred at room temperature for 15 hours. After completion of the reaction, the reaction liquid was concentrated, and the concentrate was subjected to distillation under reduced pressure (oil bath temperature: 80 ° C, pressure in a flask: 133.3 Pa) to obtain a colorless transparent liquid (di-tert-butyl (ethyl)) Mercapto) diethylaluminum 4.43 g (isolation yield: 94%).
(二第三丁基(乙基)脒基)二乙基鋁係上式(1)之R為乙基的化合物(上式(3)之化合物)。獲得之(二第三丁基(乙基)脒基)二乙基鋁的物性值如下。(Di-t-butyl(ethyl)decyl)diethylaluminum is a compound of the above formula (1) wherein R is an ethyl group (a compound of the above formula (3)). The physical property values of the obtained (di-t-butyl(ethyl)fluorenyl)diethylaluminum are as follows.
1 H-NMR(C6 D6 ,δ(ppm))； 0.35(4H,q),0.98(3H,t),1.14(18H,s),1.40(6H,t),2.14(2H,q) 1 H-NMR (C 6 D 6 , δ (ppm)); 0.35 (4H, q), 0.98 (3H, t), 1.14 (18H, s), 1.40 (6H, t), 2.14 (2H, q)
[實施例3][二第三丁基(甲基)脒基)二乙基鋁之合成] 於配備有攪拌裝置、溫度計及滴加漏斗的內容積100ml之燒瓶中，加入甲基鋰之醚溶液(1.08M,29.7mmol)並冷卻。於使燒瓶內溫度成為0～6℃之狀態在此緩慢滴加二第三丁基碳二亞胺4.50g(29.2mmol)。滴加結束後，於室溫下攪拌1小時。然後，於使燒瓶內溫度成為0～6℃之狀態在該反應液中緩慢滴加二乙基氯化鋁3.50g(29.0mmol)。滴加結束後，於室溫下攪拌15小時。反應結束後，將獲得之反應液進行矽藻土過濾並將得到之濾液濃縮，得到濃縮物。進行該濃縮物的減壓蒸餾(油浴溫度：70℃、燒瓶內的壓力：133.3Pa)，獲得無色透明液體之(二第三丁基(甲基)脒基)二乙基鋁6.29g(單離產率：85%)。[Example 3] Synthesis of [di-t-butyl(methyl)indenyl)diethylaluminum] In a 100 ml flask equipped with a stirring device, a thermometer and a dropping funnel, methyl ether was added. The solution (1.08 M, 29.7 mmol) was cooled. 4.50 g (29.2 mmol) of di-tert-butylcarbodiimide was slowly added dropwise in a state where the temperature in the flask was 0 to 6 °C. After the completion of the dropwise addition, the mixture was stirred at room temperature for 1 hour. Then, 3.50 g (29.0 mmol) of diethylaluminum chloride was slowly added dropwise to the reaction liquid while the temperature in the flask was 0 to 6 °C. After the completion of the dropwise addition, the mixture was stirred at room temperature for 15 hours. After completion of the reaction, the obtained reaction liquid was filtered through celite, and the obtained filtrate was concentrated to give a concentrate. The vacuum distillation of the concentrate was carried out (oil bath temperature: 70 ° C, pressure in a flask: 133.3 Pa) to obtain a colorless transparent liquid (di-t-butyl(methyl)decyl) diethylaluminum 6.29 g ( Isolated yield: 85%).
(二第三丁基(甲基)脒基)二乙基鋁相當於上式(5)之化合物。獲得之(二第三丁基(甲基)脒基)二乙基鋁的物性值如下。(Di-t-butyl(methyl)indenyl)diethylaluminum corresponds to the compound of the above formula (5). The physical property values of the obtained (di-t-butyl(methyl)indenyl)diethylaluminum are as follows.
1 H-NMR(C6 D6 ,δ(ppm))；0.35(4H,q),1.10(18H,s),1.41(6H,t),1.70(3H,s) 1 H-NMR (C 6 D 6 , δ (ppm)); 0.35 (4H, q), 1.10 (18H, s), 1.41 (6H, t), 1.70 (3H, s)
[實施例4][(二第三丁基(乙基)脒基)二甲基鋁之合成] 於配備有攪拌裝置、溫度計及滴加漏斗的內容積100ml之燒瓶中，加入乙基鋰之苯/環己烷溶液(0.50M,30.0mmol)並冷卻。於使燒瓶內溫度成為0～6℃之狀態在此緩慢滴加二第三丁基碳二亞胺4.63g(30.0mmol)。滴加結束後，於室溫下攪拌1小時。然後，於使燒瓶內溫度成為0～6℃之狀態在該反應液中緩慢滴加二甲基氯化鋁2.83g(30.6mmol)。滴加結束後，於室溫下攪拌15小時。反應結束後，將獲得之反應液進行矽藻土過濾並將得到之濾液濃縮，得到濃縮物。進行該濃縮物的減壓蒸餾(油浴溫度60℃、133.3Pa)，獲得無色透明液體之(二第三丁基(乙基)脒基)二甲基鋁5.40g(單離產率：75%)。[Example 4] Synthesis of [(di-t-butyl(ethyl)decyl)dimethylaluminum] In a 100 ml flask equipped with a stirring device, a thermometer, and a dropping funnel, ethyllithium was added. A benzene/cyclohexane solution (0.50 M, 30.0 mmol) was then cooled. 4.33 g (30.0 mmol) of di-tert-butylcarbodiimide was slowly added dropwise in a state where the temperature in the flask was 0 to 6 °C. After the completion of the dropwise addition, the mixture was stirred at room temperature for 1 hour. Then, 2.83 g (30.6 mmol) of dimethylaluminum chloride was slowly added dropwise to the reaction liquid while the temperature in the flask was 0 to 6 °C. After the completion of the dropwise addition, the mixture was stirred at room temperature for 15 hours. After completion of the reaction, the obtained reaction liquid was filtered through celite, and the obtained filtrate was concentrated to give a concentrate. The vacuum distillation of the concentrate (oil bath temperature 60 ° C, 133.3 Pa) was carried out to obtain 5.40 g of (di-t-butyl(ethyl)fluorenyl)dimethylaluminum as a colorless transparent liquid (isolation yield: 75 %).
(二第三丁基(乙基)脒基)二甲基鋁係上式(4)之化合物。獲得之(二第三丁基(乙基)脒基)二甲基鋁的物性值如下。(Di-t-butyl(ethyl)decyl)dimethylaluminum is a compound of the above formula (4). The physical property values of the obtained (di-t-butyl(ethyl)decyl)dimethylaluminum are as follows.
1 H-NMR(C6 D6 ,δ(ppm))；-0.23(6H,s),0.95(3H,t),1.14(18H,s),2.13(2H,q) 1 H-NMR (C 6 D 6 , δ (ppm)); -0.23 (6H, s), 0.95 (3H, t), 1.14 (18H, s), 2.13 (2H, q)
[實施例5][氧化鋁膜之製造] 使用實施例2中合成之(二第三丁基(乙基)脒基)二乙基鋁、亦即上式(3)表示之化合物作為鋁化合物，利用ALD法在基板上成膜氧化鋁膜。氧化鋁膜之成膜係使用圖1所示之裝置進行。[Example 5] [Production of Alumina Film] The compound represented by the above formula (di-t-butyl(ethyl)fluorenyl)diethylaluminum, which is represented by the above formula (3), was used as the aluminum compound. An aluminum oxide film is formed on the substrate by an ALD method. The film formation of the aluminum oxide film was carried out using the apparatus shown in Fig. 1.
圖1所示之裝置具備：氣化器1(SUS製安瓿)，係將鋁化合物2氣化；氣化器6(SUS製安瓿)，係將水7氣化而供給係反應性氣體之水蒸氣；反應器11，係具有基板15及將該基板15加熱之加熱器14，並使鋁化合物2與水蒸氣反應而在基板15上形成氧化鋁膜。真空泵浦介由流路連接至反應器11。該流路設置有：壓力計13、壓力調節閥12及收集器16。藉此，可將反應器11內的壓力調節至指定的範圍。從反應器11導出的氣體經由收集器16及真空泵浦排出到大氣中。The apparatus shown in Fig. 1 includes a gasifier 1 (an ampoule made of SUS), which vaporizes the aluminum compound 2, and a vaporizer 6 (an ampoule made of SUS), which vaporizes water 7 to supply water of a reactive gas. Vapor; the reactor 11 has a substrate 15 and a heater 14 for heating the substrate 15, and reacts the aluminum compound 2 with water vapor to form an aluminum oxide film on the substrate 15. The vacuum pump is connected to the reactor 11 via a flow path. The flow path is provided with a pressure gauge 13, a pressure regulating valve 12, and a collector 16. Thereby, the pressure in the reactor 11 can be adjusted to a specified range. The gas derived from the reactor 11 is discharged to the atmosphere via a collector 16 and a vacuum pump.
分別具備加熱器3及恆溫槽8之氣化器1及氣化器6，分別容納上述實施例2合成之鋁化合物2及水7。將氬氣供給至氣化器1中，該氬氣係利用質量流控制器4進行流量調節，並利用預熱器5進行預熱。藉此，將包含鋁化合物2之氬氣從氣化器1導入至反應器11。The vaporizer 1 and the vaporizer 6 each having the heater 3 and the constant temperature bath 8 respectively accommodate the aluminum compound 2 and the water 7 synthesized in the above-described Example 2. Argon gas is supplied to the gasifier 1, which is subjected to flow rate adjustment by the mass flow controller 4, and is preheated by the preheater 5. Thereby, argon gas containing the aluminum compound 2 is introduced from the gasifier 1 to the reactor 11.
另一方面，藉由恆溫槽8調整至一定溫度並氣化之水蒸氣從氣化器6導入至反應器11。來自氣化器1之包含鋁化合物2之氬氣、與來自氣化器6之水蒸氣交替地導入至反應器11。包含鋁化合物2之氬氣及水蒸氣的導入量分別利用閥17及閥18進行調節。包含鋁化合物2之氬氣及水蒸氣，分別和稀釋用氬氣一同導入至反應器11，該稀釋用氬氣係利用質量流控制器9進行流量調節，並利用預熱器10進行預熱。On the other hand, water vapor which is adjusted to a certain temperature by the constant temperature bath 8 and vaporized is introduced into the reactor 11 from the gasifier 6. The argon gas containing the aluminum compound 2 from the gasifier 1 is introduced into the reactor 11 alternately with the water vapor from the gasifier 6. The introduction amounts of the argon gas and the water vapor containing the aluminum compound 2 are adjusted by the valve 17 and the valve 18, respectively. Argon gas and water vapor containing the aluminum compound 2 are introduced into the reactor 11 together with the argon gas for dilution, and the flow rate is adjusted by the mass flow controller 9 by the argon gas, and preheating is performed by the preheater 10.
將鋁化合物2及水7交替地供給至反應器11，在利用加熱器14加熱至指定溫度的基板15之上形成氧化鋁膜20。圖1之裝置的運轉條件如下。The aluminum compound 2 and the water 7 are alternately supplied to the reactor 11, and the aluminum oxide film 20 is formed on the substrate 15 heated to a predetermined temperature by the heater 14. The operating conditions of the apparatus of Figure 1 are as follows.
鋁化合物2的氣化溫度(氣化器1)：90℃ 氬氣(載流氣體)流量：5mL/min(利用質量流控制器4進行調整) 鋁化合物2的供給時間：1秒 鋁化合物2的沖洗(purge)時間：5秒 水7的氣化溫度：10℃ 水7的供給時間：1秒 水7的沖洗時間：5秒 稀釋用氬氣流量：50mL/min. 基板15之材質：SiO2 /Si 基板15之大小：縱向×橫向＝20mm×20mm 基板15之溫度：300℃ 反應器11內的壓力：1333Pa 循環次數：500次(重複包含鋁化合物2之氬氣的導入、與來自氣化器6之水蒸氣的導入500次。)Gasification temperature of aluminum compound 2 (gasifier 1): 90 ° C Argon gas (carrier gas) flow rate: 5 mL / min (adjusted by mass flow controller 4) Supply time of aluminum compound 2: 1 second aluminum compound 2 Purge time: 5 seconds Water 7 gasification temperature: 10 ° C Water 7 supply time: 1 second Water 7 rinse time: 5 seconds Dilution argon flow rate: 50 mL / min. Substrate 15 material: SiO Size of 2 /Si substrate 15: longitudinal × lateral = 20 mm × 20 mm Temperature of substrate 15 : 300 ° C Pressure in reactor 11 : 1333 Pa Number of cycles: 500 (repeated introduction of argon gas containing aluminum compound 2, and gas The introduction of water vapor of the chemical device 6 was performed 500 times.)
以上述條件在基板15上形成氧化鋁膜20。使用反射式膜厚量測儀測定形成之氧化鋁膜20的厚度。又，使用XPS(X射線光電子能譜)測定裝置分析氧化鋁膜20的組成。厚度及組成分析的結果如表1所示。The aluminum oxide film 20 is formed on the substrate 15 under the above conditions. The thickness of the formed aluminum oxide film 20 was measured using a reflective film thickness measuring instrument. Further, the composition of the aluminum oxide film 20 was analyzed using an XPS (X-ray photoelectron spectroscopy) measuring device. The results of the thickness and composition analysis are shown in Table 1.
氧化鋁膜20的厚度係針對任意選擇的5處進行，並求出最大值與最小值。最大值-最小值＜10nm時，於表中顯示其算術平均值。另一方面，最大值-最小值≧10nm時，顯示最大值與最小值。The thickness of the aluminum oxide film 20 is performed at five arbitrary places, and the maximum value and the minimum value are determined. When the maximum value - minimum value < 10 nm, the arithmetic mean value is shown in the table. On the other hand, when the maximum value - the minimum value ≧ 10 nm, the maximum value and the minimum value are displayed.
[實施例6～10][氧化鋁膜之製造] 將基板15之溫度如表1所示般進行變更，除此以外，和實施例5同樣進行在基板15上形成氧化鋁膜20。形成之氧化鋁膜20的厚度及組成的分析結果如表1所示。[Examples 6 to 10] [Production of Alumina Film] The aluminum oxide film 20 was formed on the substrate 15 in the same manner as in Example 5 except that the temperature of the substrate 15 was changed as shown in Table 1. The analysis results of the thickness and composition of the formed aluminum oxide film 20 are shown in Table 1.
【表1】
實施例5～10之氧化鋁膜均無厚度之變異，並具有優異的厚度均勻性。又，已確認基板15之溫度為300～500℃之範圍內的話，氧化鋁膜的厚度無太大變化。由此可確認：藉由使用實施例2中合成之(二第三丁基(乙基)脒基)二乙基鋁，可穩定地形成氧化鋁膜。實施例10之氧化鋁膜中之氧化鋁的含量為95質量%以上，碳化鋁的含量為5質量%以下。The alumina films of Examples 5 to 10 had no variation in thickness and had excellent thickness uniformity. Further, when it is confirmed that the temperature of the substrate 15 is in the range of 300 to 500 ° C, the thickness of the aluminum oxide film does not largely change. From this, it was confirmed that the aluminum oxide film can be stably formed by using the (di-t-butyl(ethyl)fluorenyl)diethylaluminum synthesized in Example 2. The content of the alumina in the alumina film of Example 10 was 95% by mass or more, and the content of the aluminum carbide was 5% by mass or less.
[實施例11][氧化鋁膜之製造] 使用實施例3中合成之(二第三丁基(甲基)脒基)二乙基鋁、亦即上式(5)表示之化合物作為鋁化合物。除使用該鋁化合物、及將氣化器1中之鋁化合物的氣化溫度設定為80℃以外，和實施例5同樣進行在基板15上形成氧化鋁膜20。形成之氧化鋁膜20的厚度及組成的分析結果如表2所示。[Example 11] [Production of Alumina Film] The compound represented by the above formula (di-t-butyl(methyl)indenyl)diethylaluminum, which is represented by the above formula (5), was used as the aluminum compound. . The aluminum oxide film 20 was formed on the substrate 15 in the same manner as in Example 5 except that the aluminum compound was used and the vaporization temperature of the aluminum compound in the vaporizer 1 was set to 80 °C. The analysis results of the thickness and composition of the formed aluminum oxide film 20 are shown in Table 2.
[實施例12～16][氧化鋁膜之製造] 將基板15之溫度如表2所示般進行變更，除此以外，和實施例11同樣進行在基板15上形成氧化鋁膜20。形成之氧化鋁膜20的厚度及組成的分析結果如表2所示。[Examples 12 to 16] [Production of Alumina Film] The aluminum oxide film 20 was formed on the substrate 15 in the same manner as in Example 11 except that the temperature of the substrate 15 was changed as shown in Table 2. The analysis results of the thickness and composition of the formed aluminum oxide film 20 are shown in Table 2.
【表2】
實施例11～16之氧化鋁膜均無厚度之變異，並具有優異的厚度均勻性。又，已確認基板15之溫度為300～500℃之範圍內的話，氧化鋁膜的厚度無太大變化。由此可確認：藉由使用實施例3中合成之(二第三丁基(甲基)脒基)二乙基鋁，可穩定地形成氧化鋁膜。The alumina films of Examples 11 to 16 had no variation in thickness and had excellent thickness uniformity. Further, when it is confirmed that the temperature of the substrate 15 is in the range of 300 to 500 ° C, the thickness of the aluminum oxide film does not largely change. From this, it was confirmed that the aluminum oxide film can be stably formed by using the (di-t-butyl(methyl)fluorenyl)diethylaluminum synthesized in Example 3.
[實施例17][氧化鋁膜之製造] 使用實施例4中合成之(二第三丁基(乙基)脒基)二甲基鋁、亦即式(4)表示之化合物作為鋁化合物。除使用該鋁化合物、及將氣化器1中之鋁化合物的氣化溫度設定為70℃以外，和實施例5同樣進行在基板15上形成氧化鋁膜20。形成之氧化鋁膜20的厚度及組成的分析結果如表3所示。[Example 17] [Production of Alumina Film] The compound represented by the formula (4) synthesized in Example 4 (di-t-butyl(ethyl)decyl)dimethylaluminum, that is, the formula (4) was used as the aluminum compound. The aluminum oxide film 20 was formed on the substrate 15 in the same manner as in Example 5 except that the aluminum compound was used and the vaporization temperature of the aluminum compound in the vaporizer 1 was changed to 70 °C. The analysis results of the thickness and composition of the formed aluminum oxide film 20 are shown in Table 3.
[實施例18～20][氧化鋁膜之製造] 將基板15之溫度如表3所示般進行變更，除此以外，和實施例17同樣進行在基板15上形成氧化鋁膜20。形成之氧化鋁膜20的厚度及組成的分析結果如表3所示。[Examples 18 to 20] [Production of Alumina Film] The aluminum oxide film 20 was formed on the substrate 15 in the same manner as in Example 17 except that the temperature of the substrate 15 was changed as shown in Table 3. The analysis results of the thickness and composition of the formed aluminum oxide film 20 are shown in Table 3.
【表3】
實施例17～20之氧化鋁膜均無厚度之變異，並具有優異的厚度均勻性。又，已確認基板15之溫度為300～500℃之範圍內時，氧化鋁膜的厚度無變化。由此可確認：藉由使用實施例4中合成之(二第三丁基(乙基)脒基)二甲基鋁，可穩定地形成氧化鋁膜。The alumina films of Examples 17 to 20 had no variation in thickness and had excellent thickness uniformity. Further, when it was confirmed that the temperature of the substrate 15 was in the range of 300 to 500 ° C, the thickness of the aluminum oxide film did not change. From this, it was confirmed that the aluminum oxide film can be stably formed by using the (di-t-butyl(ethyl)fluorenyl)dimethylaluminum synthesized in Example 4.
[實施例21][氧化鋁膜之製造] 使用實施例1中合成之(二第三丁基(甲基)脒基)二甲基鋁、亦即式(2)表示之化合物作為鋁化合物。除使用該鋁化合物、及將氣化器1中之鋁化合物的氣化溫度設定為70℃以外，和實施例5同樣進行在基板15上形成氧化鋁膜20。形成之氧化鋁膜20的厚度及組成的分析結果如表4所示。[Example 21] [Production of Alumina Film] The compound represented by the formula (2) synthesized in Example 1 (di-t-butyl(methyl)indenyl)dimethylaluminum, that is, the formula (2) was used as the aluminum compound. The aluminum oxide film 20 was formed on the substrate 15 in the same manner as in Example 5 except that the aluminum compound was used and the vaporization temperature of the aluminum compound in the vaporizer 1 was changed to 70 °C. The analysis results of the thickness and composition of the formed aluminum oxide film 20 are shown in Table 4.
[實施例22～24][氧化鋁膜之製造] 將基板15之溫度如表4所示般進行變更，除此以外，和實施例21同樣進行在基板15上形成氧化鋁膜20。形成之氧化鋁膜20的厚度及組成的分析結果如表4所示。[Examples 22 to 24] [Production of Alumina Film] The aluminum oxide film 20 was formed on the substrate 15 in the same manner as in Example 21 except that the temperature of the substrate 15 was changed as shown in Table 4. The analysis results of the thickness and composition of the formed aluminum oxide film 20 are shown in Table 4.
【表4】
實施例21～24之氧化鋁膜均無厚度之變異，並具有優異的厚度均勻性。又，已確認基板15之溫度為300～500℃之範圍內時，氧化鋁膜的厚度無變化。由此可確認：藉由使用實施例1中合成之二第三丁基(甲基)脒基)二甲基鋁，可穩定地形成氧化鋁膜。The alumina films of Examples 21 to 24 had no variation in thickness and had excellent thickness uniformity. Further, when it was confirmed that the temperature of the substrate 15 was in the range of 300 to 500 ° C, the thickness of the aluminum oxide film did not change. From this, it was confirmed that the aluminum oxide film can be stably formed by using the tributyl(methyl)fluorenyl)dimethylaluminum synthesized in Example 1.
[比較例1][(二異丙基(甲基)脒基)二甲基鋁之合成] 於配備有攪拌裝置、溫度計及滴加漏斗的內容積50ml之燒瓶中，加入三甲基鋁2.00g(27.7mmol)、及己烷25mL並冷卻。於使燒瓶內溫度成為0～6℃之狀態在此緩慢滴加二異丙基碳二亞胺3.50g(27.7mmol)。滴加結束後，於室溫下攪拌15小時。反應結束後，將該反應液濃縮，並將濃縮物進行減壓蒸餾(油浴溫度70℃、燒瓶內的壓力：133.3Pa)，獲得透明液體之(二異丙基(甲基)脒基)二甲基鋁4.94g(單離產率：90質量%)。[Comparative Example 1] Synthesis of [(diisopropyl(methyl)indenyl)dimethylaluminum] In a 50 ml flask equipped with a stirring device, a thermometer and a dropping funnel, trimethylaluminum 2.00 was added. g (27.7 mmol) and 25 mL of hexane were cooled. 3.50 g (27.7 mmol) of diisopropylcarbodiimide was slowly added dropwise to the temperature in the flask at 0 to 6 °C. After the completion of the dropwise addition, the mixture was stirred at room temperature for 15 hours. After completion of the reaction, the reaction liquid was concentrated, and the concentrate was subjected to distillation under reduced pressure (oil bath temperature: 70 ° C, pressure in a flask: 133.3 Pa) to obtain a transparent liquid (diisopropyl(methyl)decyl). Dimethylaluminum 4.94 g (isolation yield: 90% by mass).
(二異丙基(甲基)脒基)二甲基鋁係以下列化學式表示。獲得之(二異丙基(甲基)脒基)二甲基鋁的物性值如下。(Diisopropyl(methyl)indenyl)dimethylaluminum is represented by the following chemical formula. The physical property values of (diisopropyl(methyl)indenyl)dimethylaluminum obtained were as follows.
【化學式9】 [Chemical Formula 9]
1 H-NMR(C6 D6 ,δ(ppm))；-0.23(6H,s),0.96(12H,d)1.26(3H,t),3.09-3.15(2H,m) 1 H-NMR (C 6 D 6 , δ (ppm)); -0.23 (6H, s), 0.96 (12H, d) 1.26 (3H, t), 3.09 - 3.15 (2H, m)
[比較例2][氧化鋁膜之製造] 使用比較例1中合成之(二異丙基(甲基)脒基)二甲基鋁作為鋁化合物。除使用該鋁化合物、及將氣化器1中之鋁化合物的氣化溫度設定為50℃以外，和實施例5同樣進行在基板15上形成氧化鋁膜20。形成之氧化鋁膜20的厚度及組成的分析結果如表5所示。[Comparative Example 2] [Production of Alumina Film] The (diisopropyl(methyl)indenyl)dimethylaluminum synthesized in Comparative Example 1 was used as an aluminum compound. The aluminum oxide film 20 was formed on the substrate 15 in the same manner as in Example 5 except that the aluminum compound was used and the vaporization temperature of the aluminum compound in the vaporizer 1 was set to 50 °C. The analysis results of the thickness and composition of the formed aluminum oxide film 20 are shown in Table 5.
[比較例3][氧化鋁膜之製造] 將基板15之溫度如表5所示般進行變更，除此以外，和比較例2同樣進行在基板15上形成氧化鋁膜20。形成之氧化鋁膜20的厚度及組成的分析結果如表5所示。[Comparative Example 3] [Production of Alumina Film] The aluminum oxide film 20 was formed on the substrate 15 in the same manner as in Comparative Example 2 except that the temperature of the substrate 15 was changed as shown in Table 5. The analysis results of the thickness and composition of the formed aluminum oxide film 20 are shown in Table 5.
【表5】
比較例2、3之氧化鋁膜兩者的厚度之變異大，相較於各實施例厚度均勻性差。如此厚度之變異大的原因，據認為係由於鋁化合物的熱穩定性低，故熱分解進行不均勻，成膜速度的變異變大。The variations in the thickness of both of the alumina films of Comparative Examples 2 and 3 were large, and the thickness uniformity was inferior to those of the respective examples. The reason why the variation in the thickness is large is considered to be because the thermal stability of the aluminum compound is low, so that the thermal decomposition proceeds unevenly, and the variation in the film formation speed becomes large.
[比較例4][(二甲基醯胺)二乙基鋁之合成] 於配備有攪拌裝置、溫度計及滴加漏斗的內容積50ml之燒瓶中，加入二甲基醯胺鋰1.36g(26.7mmol)、及戊烷25mL並冷卻。於使燒瓶內溫度成為0～6℃之狀態在此緩慢滴加二乙基氯化鋁3.20g(26.5mmol)。滴加結束後，於室溫下攪拌15小時。反應結束後，將獲得之白色懸浮液進行過濾，並將該濾液濃縮。對獲得之濃縮物進行減壓蒸餾(油浴溫度90℃、燒瓶內的壓力：133.3Pa)，獲得透明液體之(二甲基醯胺)二乙基鋁3.02g(單離產率：82質量%)。[Comparative Example 4] Synthesis of [(dimethylguanamine) diethylaluminum] In a 50 ml flask equipped with a stirrer, a thermometer and a dropping funnel, lithium dimethyl guanamine 1.36 g (26.7) was added. Methyl), and pentane 25 mL and cooled. 3.20 g (26.5 mmol) of diethylaluminum chloride was slowly added dropwise thereto in a state where the temperature in the flask was 0 to 6 °C. After the completion of the dropwise addition, the mixture was stirred at room temperature for 15 hours. After the reaction was completed, the obtained white suspension was filtered, and the filtrate was concentrated. The obtained concentrate was subjected to distillation under reduced pressure (oil bath temperature: 90 ° C, pressure in a flask: 133.3 Pa) to obtain a transparent liquid of (dimethylamine) diethylaluminum (3.02 g) (isolation yield: 82 mass) %).
獲得之(二甲基醯胺)二乙基鋁的物性值如下。The physical property values of (dimethyl decylamine) diethylaluminum obtained were as follows.
1 H-NMR(C6 D6 ,δ(ppm))；0.10(4H,q),1.27(6H,t)2.10(6H,s) 1 H-NMR (C 6 D 6 , δ (ppm)); 0.10 (4H, q), 1.27 (6H, t) 2.10 (6H, s)
[比較例5][氧化鋁膜之製造] 使用比較例4中合成之(二甲基醯胺)二乙基鋁作為鋁化合物。除使用該鋁化合物、及將氣化器1中之鋁化合物的氣化溫度設定為70℃以外，和實施例5同樣進行在基板15上形成氧化鋁膜20。形成之氧化鋁膜20的厚度及組成的分析結果如表6所示。[Comparative Example 5] [Production of Alumina Film] The (dimethyl decylamine) diethyl aluminum synthesized in Comparative Example 4 was used as the aluminum compound. The aluminum oxide film 20 was formed on the substrate 15 in the same manner as in Example 5 except that the aluminum compound was used and the vaporization temperature of the aluminum compound in the vaporizer 1 was changed to 70 °C. The analysis results of the thickness and composition of the formed aluminum oxide film 20 are shown in Table 6.
[比較例6、7][氧化鋁膜之製造] 將基板15之溫度如表6所示般進行變更，除此以外，和比較例5同樣進行在基板15上形成氧化鋁膜20。形成之氧化鋁膜20的厚度及組成的分析結果如表6所示。[Comparative Examples 6 and 7] [Production of Alumina Film] The aluminum oxide film 20 was formed on the substrate 15 in the same manner as in Comparative Example 5 except that the temperature of the substrate 15 was changed as shown in Table 6. The analysis results of the thickness and composition of the formed aluminum oxide film 20 are shown in Table 6.
【表6】
比較例5之氧化鋁膜其厚度之變異小。但，比較例6、7之氧化鋁膜兩者的厚度之變異大，相較於各實施例厚度均勻性差。如此厚度之變異大的原因，據認為係由於鋁化合物的熱穩定性低，故熱分解進行不均勻，成膜速度的變異變大。由表6所示之結果可確認：比較例4之鋁化合物，在基板之溫度變動的情況下，氧化鋁膜的厚度之變異變大。因此，無法穩定地製造厚度之變異減小之氧化鋁膜。The aluminum oxide film of Comparative Example 5 had a small variation in thickness. However, the variations in the thickness of both of the alumina films of Comparative Examples 6 and 7 were large, and the thickness uniformity was inferior to those of the respective examples. The reason why the variation in the thickness is large is considered to be because the thermal stability of the aluminum compound is low, so that the thermal decomposition proceeds unevenly, and the variation in the film formation speed becomes large. From the results shown in Table 6, it was confirmed that the aluminum compound of Comparative Example 4 had a large variation in the thickness of the aluminum oxide film when the temperature of the substrate fluctuated. Therefore, an alumina film having a reduced variation in thickness cannot be stably produced.
上述各實施例中所使用之上式(2)～(5)表示之鋁化合物，安全性也足夠優異。又，由於以上述條件形成了氧化鋁薄膜，式(2)～(5)表示之鋁化合物與反應性氣體的反應性良好。亦可知含有上式(2)～(5)表示之鋁化合物的蒸氣於基板表面的吸附性優異。進一步，藉由將基板之溫度設定為300～500℃，可減小厚度的變化，同時可形成氧化鋁之純度高的氧化鋁膜。亦即，可製造品質優良的氧化鋁膜。 [產業上利用性]The aluminum compound represented by the above formulas (2) to (5) used in each of the above examples is sufficiently excellent in safety. Moreover, since the aluminum oxide film was formed under the above conditions, the reactivity of the aluminum compound represented by the formulas (2) to (5) with the reactive gas was good. It is also known that the vapor containing the aluminum compound represented by the above formulas (2) to (5) is excellent in the adsorptivity on the surface of the substrate. Further, by setting the temperature of the substrate to 300 to 500 ° C, the change in thickness can be reduced, and an aluminum oxide film having a high purity of alumina can be formed. That is, an alumina film of excellent quality can be produced. [Industrial use]
本發明提供一種能穩定地製造厚度之變異減小之氧化鋁膜的氧化鋁膜之製造方法。並提供適合用於該製造方法的製造原料、及鋁化合物。The present invention provides a method for producing an alumina film which can stably produce an aluminum oxide film having a reduced variation in thickness. A raw material for production and an aluminum compound suitable for use in the production method are provided.
1、6‧‧‧氣化器
2‧‧‧鋁化合物
3、14‧‧‧加熱器
4、9‧‧‧質量流控制器
5、10‧‧‧預熱器
8‧‧‧恆溫槽
11‧‧‧反應器
12‧‧‧壓力調節閥
13‧‧‧壓力計
15‧‧‧基板
16‧‧‧收集器
17、18‧‧‧閥
20‧‧‧氧化鋁膜1, 6‧‧‧ gasifier
2‧‧‧Aluminum compound
3, 14‧‧‧ heater
4, 9‧‧‧ mass flow controller
5, 10‧‧‧ preheater
8‧‧‧ thermostat
11‧‧‧Reactor
12‧‧‧pressure regulating valve
13‧‧‧ Pressure gauge
15‧‧‧Substrate
16‧‧‧ Collector
17, 18‧‧‧ Valve
20‧‧‧Alumina film
[圖1]係氧化鋁膜之製造裝置的示意圖。Fig. 1 is a schematic view showing a manufacturing apparatus of an alumina film.
無no
Claims (7)
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| JP2015162347 | 2015-08-20 | ||
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