JP2010229112A - COBALT COMPLEX CONTAINING beta-DIKETONATO GROUP AS LIGAND AND METHOD FOR PRODUCING COBALT-CONTAINING THIN FILM USING THE SAME - Google Patents
COBALT COMPLEX CONTAINING beta-DIKETONATO GROUP AS LIGAND AND METHOD FOR PRODUCING COBALT-CONTAINING THIN FILM USING THE SAME Download PDFInfo
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- 150000004700 cobalt complex Chemical class 0.000 title claims abstract description 39
- 239000010409 thin film Substances 0.000 title claims abstract description 29
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 13
- 239000003446 ligand Substances 0.000 title abstract description 10
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 34
- 239000010941 cobalt Substances 0.000 claims abstract description 34
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 15
- 239000007789 gas Substances 0.000 claims description 15
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 11
- 238000000151 deposition Methods 0.000 claims description 8
- 239000000758 substrate Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 4
- 230000008016 vaporization Effects 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims 1
- 238000005979 thermal decomposition reaction Methods 0.000 claims 1
- 239000002184 metal Substances 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 14
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 239000010408 film Substances 0.000 description 6
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- 239000006200 vaporizer Substances 0.000 description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- RTDZKQXFYHZOKZ-UHFFFAOYSA-N 2,6-dimethyl-2-trimethylsilyloxyheptane-3,5-dione Chemical compound CC(C)C(=O)CC(=O)C(C)(C)O[Si](C)(C)C RTDZKQXFYHZOKZ-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001869 cobalt compounds Chemical class 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000000231 atomic layer deposition Methods 0.000 description 2
- 150000001868 cobalt Chemical class 0.000 description 2
- ZBYYWKJVSFHYJL-UHFFFAOYSA-L cobalt(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Co+2].CC([O-])=O.CC([O-])=O ZBYYWKJVSFHYJL-UHFFFAOYSA-L 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 150000004696 coordination complex Chemical class 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- SYBYTAAJFKOIEJ-UHFFFAOYSA-N 3-Methylbutan-2-one Chemical compound CC(C)C(C)=O SYBYTAAJFKOIEJ-UHFFFAOYSA-N 0.000 description 1
- UZTKEDFSHYALEH-UHFFFAOYSA-N 6-trimethylsilyloxyoctane-3,5-dione Chemical compound CCC(C(CC(CC)=O)=O)O[Si](C)(C)C UZTKEDFSHYALEH-UHFFFAOYSA-N 0.000 description 1
- YDLSIWIVJBEBJO-UHFFFAOYSA-N C[Si](C)(C)C1(C=CC=C1)[Co]C1(C=CC=C1)[Si](C)(C)C Chemical compound C[Si](C)(C)C1(C=CC=C1)[Co]C1(C=CC=C1)[Si](C)(C)C YDLSIWIVJBEBJO-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 239000003708 ampul Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- AEVRNKXPLOTCBW-UHFFFAOYSA-N carbon monoxide;cobalt;cyclopenta-1,3-diene Chemical group [Co].[O+]#[C-].[O+]#[C-].C=1C=C[CH-]C=1 AEVRNKXPLOTCBW-UHFFFAOYSA-N 0.000 description 1
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 description 1
- BKFAZDGHFACXKY-UHFFFAOYSA-N cobalt(II) bis(acetylacetonate) Chemical compound [Co+2].CC(=O)[CH-]C(C)=O.CC(=O)[CH-]C(C)=O BKFAZDGHFACXKY-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
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- 230000018109 developmental process Effects 0.000 description 1
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- -1 dimethyl-2-trimethylsilyloxy-3,5-heptanedione Chemical compound 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- LZFDOCGPXDEJNG-UHFFFAOYSA-N methyl 2-methyl-2-trimethylsilyloxypropanoate Chemical compound COC(=O)C(C)(C)O[Si](C)(C)C LZFDOCGPXDEJNG-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000000410 reductive pyrolysis Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- ODZPKZBBUMBTMG-UHFFFAOYSA-N sodium amide Chemical compound [NH2-].[Na+] ODZPKZBBUMBTMG-UHFFFAOYSA-N 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
本発明は、新規なβ−ジケトナト配位子を有するコバルト錯体、及び該コバルト錯体を用いて化学気相蒸着法（ＣＶＤ法）によりコバルト含有薄膜を製造する方法に関する。 The present invention relates to a cobalt complex having a novel β-diketonato ligand and a method for producing a cobalt-containing thin film by chemical vapor deposition (CVD) using the cobalt complex.
近年、半導体、電子部品等の分野の材料として、コバルト化合物に関しては、多くの研究、開発がなされている。
これまで提案されてきたコバルト化合物としては、例えば、ビス（アセチルアセトナト）コバルト（例えば、非特許文献１参照）、オクタカルボニルジコバルト（例えば、非特許文献２参照）コバルトシクロペンタジエニルジカルボニル（例えば、非特許文献３参照）やビス（トリメチルシリルシクロペンタジエニル）コバルト（例えば、特許文献１参照）が開示されている。
In recent years, many researches and developments have been made on cobalt compounds as materials in the fields of semiconductors and electronic components.
Examples of cobalt compounds that have been proposed so far include, for example, bis (acetylacetonato) cobalt (see, for example, Non-Patent Document 1), octacarbonyldicobalt (for example, see Non-Patent Document 2), and cobalt cyclopentadienyl dicarbonyl. (For example, refer nonpatent literature 3) and bis (trimethylsilyl cyclopentadienyl) cobalt (for example, refer patent document 1) are indicated.
従来のコバルト錯体、例えば、非特許文献１に記載のコバルト錯体は、融点が高いためＣＶＤ用原料としては採用されにくいという問題があった。又、非特許文献２及び３のコバルト錯体は、熱安定性が低く、分解し易いという欠点があった。これを改良したコバルト錯体として、特許文献１のコバルト錯体が提案されているが、コバルト化合物やその配位子の合成法が煩雑であり、又、その合成過程で発火性のナトリウムやｎ−ブチルリチウムを使用する等、工業的に使用する場合には問題となっていた。
Conventional cobalt complexes, for example, the cobalt complex described in
本発明の課題は、即ち、低い融点を有し、且つ水分や空気に対して安定性に優れ、ＣＶＤ法による金属薄膜形成に適したβ−ジケトナト基を配位子として有するコバルト錯体を提供するものである。又、本発明の課題は、当該コバルト錯体を用いてコバルト含有薄膜を製造する方法を提供するものでもある。 An object of the present invention is to provide a cobalt complex having a β-diketonato group as a ligand, which has a low melting point and is excellent in stability to moisture and air and is suitable for forming a metal thin film by a CVD method. Is. Moreover, the subject of this invention is also providing the method of manufacturing a cobalt containing thin film using the said cobalt complex.
本発明の課題は、一般式（Ｉ） The subject of the present invention is the general formula (I)
（式中、Ｘは、一般式（ＩＩ） (Wherein X represents the general formula (II)
で示される基（式中、Ｒａ１は及びＲａ２は、炭素原子数１〜５の直鎖又は分枝状のアルキル基、Ｒｂ、Ｒｃ及びＲｄは、炭素原子数１〜５の直鎖又は分枝状のアルキル基を示す。）、Ｙは炭素原子数１〜８の直鎖又は分枝状のアルキル基、Ｚは、水素原子又は炭素原子数１〜４のアルキル基を示す。）
で示されるβ-ジケトナト基を配位子として有するコバルト錯体によって解決される。
Wherein R a1 and R a2 are linear or branched alkyl groups having 1 to 5 carbon atoms, and R b , R c and R d are 1 to 5 carbon atoms. A linear or branched alkyl group), Y represents a linear or branched alkyl group having 1 to 8 carbon atoms, and Z represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. . )
And a cobalt complex having a β-diketonato group as a ligand.
本発明の課題は、又、当該コバルト錯体をコバルト供給源として用いて、化学気相蒸着法によりコバルト含有薄膜を製造する方法によっても解決される。 The problem of the present invention is also solved by a method for producing a cobalt-containing thin film by chemical vapor deposition using the cobalt complex as a cobalt supply source.
本発明により、ＣＶＤ法によりコバルト原子を含有するコバルト含有薄膜を形成させる際に使用可能な、コバルト錯体を提供することが出来る。又、当該コバルト錯体を用いてコバルト含有薄膜を製造する方法も提供することが出来る。 The present invention can provide a cobalt complex that can be used when a cobalt-containing thin film containing cobalt atoms is formed by a CVD method. Moreover, the method of manufacturing a cobalt containing thin film using the said cobalt complex can also be provided.
本発明のβ−ジケトナト基を配位子として有するコバルト錯体は、前記の一般式（Ｉ）で示される。その一般式（Ｉ）において、Ｘは一般式（ＩＩ）で示される基（Ｒａ１、Ｒａ２、Ｒｂ、Ｒｃ及びＲｄは、例えば、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｔ−ブチル基、ペンチル基等の炭素原子数１〜５の直鎖又は分枝状のアルキル基を示す。）；Ｙは、該一般式（ＩＩ）で示される基又はメチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｔ−ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基等の炭素原子数１〜８の直鎖又は分枝状のアルキル基；Ｚは水素原子、又はメチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｔ−ブチル基等の炭素原子数１〜４の直鎖又は分枝状のアルキル基を示す。
The cobalt complex having the β-diketonato group of the present invention as a ligand is represented by the above general formula (I). In the general formula (I), X represents a group represented by the general formula (II) (R a1 , R a2 , R b , R c and R d are, for example, methyl group, ethyl group, n-propyl group, isopropyl A straight chain or branched alkyl group having 1 to 5 carbon atoms such as a group, n-butyl group, isobutyl group, t-butyl group, pentyl group, etc.); Y represents the general formula (II) 1 to 8 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, pentyl group, hexyl group, heptyl group, octyl group A linear or branched alkyl group of the above; Z is a hydrogen atom or a C 1 -
前記β−ジケトナト基上の置換基の好ましい態様としては、Ｒａ１は及びＲａ２が炭素原子数１〜５の直鎖又は分枝状のアルキル基、Ｒｂ、Ｒｃ及びＲｄがメチル基であり、Ｙは炭素原子数１〜８の直鎖又は分枝状のアルキル基であり、Ｚが水素原子である。 As a preferable embodiment of the substituent on the β-diketonato group, R a1 and R a2 are linear or branched alkyl groups having 1 to 5 carbon atoms, R b , R c and R d are methyl groups. Y is a linear or branched alkyl group having 1 to 8 carbon atoms, and Z is a hydrogen atom.
本発明の該金属錯体が有するβ−ジケトナト基（配位子）の元となるβ−ジケトンは、公知の方法により容易に合成が可能な化合物である（例えば、特許文献２参照）。 The β-diketone that is the basis of the β-diketonato group (ligand) of the metal complex of the present invention is a compound that can be easily synthesized by a known method (see, for example, Patent Document 2).
本発明のβ−ジケトナト基を配位子として有する金属錯体の具体例としては、例えば、式（ＩＩＩ）から式（ＶＩＩＩ）で示される。 Specific examples of the metal complex having the β-diketonato group of the present invention as a ligand are represented by, for example, formulas (III) to (VIII).
なお、ＣＶＤ法においては、コバルト含有薄膜形成のためにコバルト錯体を気化させる必要があるが、本発明のβ−ジケトナト基を配位子として有するコバルト錯体を気化させる方法としてはコバルト錯体を適当な溶媒（例えば、ヘキサン、オクタン等の脂肪族炭化水素類；トルエン等の芳香族炭化水素類；テトラヒドロフラン、ジブチルエーテル等のエーテル類等が挙げられる。）に希釈した溶液を液体搬送用ポンプで気化室に導入して気化させる方法（溶液法）も使用出来る。 In the CVD method, it is necessary to vaporize a cobalt complex in order to form a cobalt-containing thin film. However, as a method for vaporizing a cobalt complex having a β-diketonato group as a ligand of the present invention, a cobalt complex is suitable. The solution diluted with a solvent (for example, aliphatic hydrocarbons such as hexane and octane; aromatic hydrocarbons such as toluene; ethers such as tetrahydrofuran and dibutyl ether) is vaporized by a pump for liquid transportation. It is also possible to use a method (solution method) in which it is introduced into and vaporized.
本発明のコバルト錯体を使用しての基板上へのコバルトの蒸着方法としては、例えば、通常のＣＶＤ法、即ち、コバルト錯体を気化させ、この気化させたコバルト錯体を熱分解させる方法や水素源（水素ガス等の還元性ガス）との反応による方法で、基板上に堆積させることによりコバルト含有薄膜を生成させることができる。又、コバルト錯体と水素ガスをＣＶＤチャンバー内に交互に導入し、コバルト含有薄膜を成膜するパルスＣＶＤ法、あるいは、コバルト錯体をチャンバー内に導入した後、一旦排気し、余分なコバルト錯体を留去させた後、続いて水素ガスを導入、排気する操作を繰り返すことにより、コバルト原子を一層ずつ成膜する原子層堆積法（ＡＬＤ法）によっても、コバルト含有薄膜を生成させることができる。 Examples of a method for depositing cobalt on a substrate using the cobalt complex of the present invention include, for example, a normal CVD method, that is, a method of vaporizing a cobalt complex and thermally decomposing the vaporized cobalt complex, or a hydrogen source. A cobalt-containing thin film can be produced by depositing on a substrate by a method by reaction with (reducing gas such as hydrogen gas). Alternatively, a cobalt complex and hydrogen gas are alternately introduced into the CVD chamber to form a cobalt-containing thin film, or a pulsed CVD method in which a cobalt-containing thin film is formed. Then, by repeating the operation of introducing and exhausting hydrogen gas, the cobalt-containing thin film can be produced also by an atomic layer deposition method (ALD method) in which cobalt atoms are formed one by one.
当該有機コバルト錯体と水素源を用いて金属コバルト膜を蒸着させる際には、反応系内の圧力は、好ましくは１Ｐａ〜２００ｋＰａ、更に好ましくは１０Ｐａ〜１１０ｋＰａであり、成膜対象物の温度は、好ましくは１５０〜７００℃、更に好ましくは２００〜５００℃である。又、水素ガス等の還元性ガスによる金属薄膜を蒸着させる際の全ガス量に対する還元性ガスの含有割合は、好ましくは５〜９９容量％、更に好ましくは１０〜９５容量％である。 When the metal cobalt film is deposited using the organic cobalt complex and the hydrogen source, the pressure in the reaction system is preferably 1 Pa to 200 kPa, more preferably 10 Pa to 110 kPa, and the temperature of the film formation target is Preferably it is 150-700 degreeC, More preferably, it is 200-500 degreeC. Further, the content ratio of the reducing gas with respect to the total gas amount when the metal thin film is deposited by the reducing gas such as hydrogen gas is preferably 5 to 99% by volume, more preferably 10 to 95% by volume.
前記コバルト含有薄膜を加熱処理する際には、コバルト含有薄膜の存在している雰囲気を不活性雰囲気又は還元雰囲気とすることが望ましく、例えば、窒素、ヘリウム、アルゴン等の不活性ガスによって不活性雰囲気又は、水素ガス等の還元性ガスにより還元雰囲気にて好適に行われる。なお、これらのガスは混合して使用しても構わない。 When the cobalt-containing thin film is heat-treated, it is desirable that the atmosphere in which the cobalt-containing thin film exists is an inert atmosphere or a reducing atmosphere, for example, an inert atmosphere such as nitrogen, helium, or argon. Alternatively, it is suitably performed in a reducing atmosphere with a reducing gas such as hydrogen gas. These gases may be used as a mixture.
加熱処理する温度は、好ましくは１００〜１０００℃、更に好ましくは１５０〜９００℃であり、圧力は、１Ｐａ〜２００ｋＰａ、更に好ましくは１０Ｐａ〜１１０ｋＰａである。なお、還元性ガスを使用した場合には、特に当該圧力範囲において、その還元能力を確実に発揮させることができるとともに、後処理の繁雑さを解消することができる。 The temperature for the heat treatment is preferably 100 to 1000 ° C., more preferably 150 to 900 ° C., and the pressure is 1 Pa to 200 kPa, more preferably 10 Pa to 110 kPa. In addition, when reducing gas is used, especially in the said pressure range, while being able to exhibit the reducing capability reliably, the complexity of post-processing can be eliminated.
加熱処理時間は、処理条件（使用したコバルト錯体の種類、温度、圧力、ガスの種類等）によって、適宜調節するが、１０〜３６００秒の加熱処理を行うことで生産性の向上を損なうことなく、本発明のコバルト含有薄膜が製造できる。 The heat treatment time is appropriately adjusted depending on the treatment conditions (type of cobalt complex used, temperature, pressure, type of gas, etc.), but without impairing productivity improvement by performing heat treatment for 10 to 3600 seconds. The cobalt-containing thin film of the present invention can be produced.
次に、実施例を挙げて本発明を具体的に説明するが、本発明の範囲はこれらに限定されるものではない。 Next, the present invention will be specifically described with reference to examples, but the scope of the present invention is not limited thereto.
参考例１（２，６−ジメチル−２−トリメチルシリルオキシ−３，５−ヘプタンジオンの合成）
攪拌装置、温度計及び滴下漏斗を備えた内容積５００ｍｌのフラスコに、ナトリウムアミド１３．７ｇ（０．３５１ｍｏｌ）及びヘキサン２００ｍｌを加え、攪拌させながら２−トリメチルシリルオキシ−２−メチルプロピオン酸メチル２６．７ｇ（０．１４０ｍｏｌ）を滴下した。次いで、攪拌させながら３−メチル−２−ブタノン１２．１ｇ（０．１４１ｍｏｌ）を滴下し、１５℃で１時間反応させた。反応終了後、酢酸を加えて弱酸性にした後、有機層を水で洗浄後、無水硫酸ナトリウムで乾燥させた。濾過後、濾液を減圧蒸留（１０１℃、１０６７Ｐａ）し、２，６−ジメチル−２−トリメチルシリルオキシ−３，５−ヘプタンジオン１８．８ｇを得た（単離収率：５５％）。
２，６−ジメチル−２−トリメチルシリルオキシ−３，５−ヘプタンジオンの物性値は以下の通りであった。
Reference Example 1 (Synthesis of 2,6-dimethyl-2-trimethylsilyloxy-3,5-heptanedione)
13.7 g (0.351 mol) of sodium amide and 200 ml of hexane were added to a flask having an internal volume of 500 ml equipped with a stirrer, a thermometer and a dropping funnel, and methyl 2-trimethylsilyloxy-2-methylpropionate 26. 7 g (0.140 mol) was added dropwise. Next, 12.1 g (0.141 mol) of 3-methyl-2-butanone was added dropwise with stirring and reacted at 15 ° C. for 1 hour. After completion of the reaction, acetic acid was added to make it weakly acidic, and the organic layer was washed with water and dried over anhydrous sodium sulfate. After filtration, the filtrate was distilled under reduced pressure (101 ° C., 1067 Pa) to obtain 18.8 g of 2,6-dimethyl-2-trimethylsilyloxy-3,5-heptanedione (isolated yield: 55%).
The physical properties of 2,6-dimethyl-2-trimethylsilyloxy-3,5-heptanedione were as follows.
１Ｈ−ＮＭＲ（ＣＤＣｌ３，δ（ｐｐｍ））；１．１４（６Ｈ，ｄ），１．３９（６Ｈ，ｓ）、２．４４〜２．５０（０．８５Ｈ，ｍ），２．６４〜２．６９（０．１５Ｈ，ｍ）、３．７７（０．３Ｈ，ｓ），５．９７（０．８５Ｈ，ｓ），１５．５１（０．８５Ｈ，ｓ）
ＩＲ（ｎｅａｔ（ｃｍ−１））；２９７１，１６０６（ｂｒ），１２５３，１１９９，１０４５，８４２
（なお、１６０６ｃｍ−１のピークは、β−ジケトン特有のピークである。）
ＭＳ（ｍ／ｅ）；２４４
1 H-NMR (CDCl 3 , δ (ppm)); 1.14 (6H, d), 1.39 (6H, s), 2.44 to 2.50 (0.85 H, m), 2.64 -2.69 (0.15H, m), 3.77 (0.3H, s), 5.97 (0.85H, s), 15.51 (0.85H, s)
IR (neat (cm −1 )); 2971, 1606 (br), 1253, 1199, 1045, 842
(The peak at 1606 cm −1 is a peak peculiar to β-diketone.)
MS (m / e); 244
実施例１（ビス（２，６−ジメチル−２−トリメチルシリルオキシ−３，５−ヘプタンジオナトコバルト（ＩＩ）（以下、Ｃｏ（ｓｏｐｄ）２と称する）の合成）
攪拌装置、温度計及び滴下漏斗を備えた内容積２００ｍｌのフラスコに、２８％ナトリウムメトキシドのメタノール溶液５．０８ｇ（２６.３ｍｍｏｌ）を加え、液温を４℃に保ちながら、２，６−ジメチル−２−トリメチルシリルオキシ−３，５−ヘプタンジオン７．０２ｇ（２８.７ｍｍｏｌ）をゆるやかに滴下し、同温度で３０分間攪拌させた。次いで、酢酸コバルト（ＩＩ）４水和物３.１４ｇ（１２.６ｍｍｏｌ）をメタノール１５ｍｌに溶解させた溶液を滴下し、攪拌しながら室温で３０分間反応させた。反応終了後、反応液にヘキサン３０ｍｌ及び水３０ｍｌを加えた後、有機層を分液した。該有機層を水で洗浄し、無水硫酸ナトリウムで乾燥させた。濾過後、濾液を濃縮して、濃縮物を減圧蒸留（１７０℃、１６Ｐａ）し、赤紫色粘性液体として、ビス（２，６−ジメチル−２−トリメチルシリルオキシ−３，５−ヘプタンジオナト）コバルト（ＩＩ）６.５ｇを得た（単離収率；９４％）。
ビス（２，６−ジメチル−２−トリメチルシリルオキシ−３，５−ヘプタンジオナト）コバルト（ＩＩ）は、以下の物性値で示される新規な化合物である。
Example 1 (Synthesis of bis (2,6-dimethyl-2-trimethylsilyloxy-3,5-heptanedionatocobalt (II) (hereinafter referred to as Co (sopd) 2 ))
To a 200 ml flask equipped with a stirrer, thermometer and dropping funnel, 5.08 g (26.3 mmol) of 28% sodium methoxide in methanol was added, and while maintaining the liquid temperature at 4 ° C., 2,6- 7.02 g (28.7 mmol) of dimethyl-2-trimethylsilyloxy-3,5-heptanedione was gently added dropwise and stirred at the same temperature for 30 minutes. Subsequently, a solution in which 3.14 g (12.6 mmol) of cobalt (II) acetate tetrahydrate was dissolved in 15 ml of methanol was dropped, and the mixture was reacted at room temperature for 30 minutes with stirring. After completion of the reaction, 30 ml of hexane and 30 ml of water were added to the reaction solution, and then the organic layer was separated. The organic layer was washed with water and dried over anhydrous sodium sulfate. After filtration, the filtrate is concentrated, and the concentrate is distilled under reduced pressure (170 ° C., 16 Pa) to give bis (2,6-dimethyl-2-trimethylsilyloxy-3,5-heptanedionato) cobalt (II) as a reddish purple viscous liquid. ) 6.5 g was obtained (isolated yield; 94%).
Bis (2,6-dimethyl-2-trimethylsilyloxy-3,5-heptanedionato) cobalt (II) is a novel compound represented by the following physical property values.
ＩＲ（ｎｅａｔ（ｃｍ−１））；２９６４，１５７４，１５０９，１４１７，１２５２，１１９５，１０４８，８９１，８４０
（β−ジケトン特有のピーク（１６０６ｃｍ−１）が消失し、β−ジケトナト特有のピーク（１５７４ｃｍ−１）が観察された）
元素分析（Ｃ２４Ｈ４６Ｏ６Ｓｉ２Ｃｏ）；炭素：５２．９％，水素：８．５３％，コバルト：１０．７％
（理論値；炭素：５２．８％，水素：８．５０％，コバルト：１０．８％）
IR (neat (cm −1 )); 2964, 1574, 1509, 1417, 1252, 1195, 1048, 891, 840
(A peak peculiar to β-diketone (1606 cm −1 ) disappeared, and a peak peculiar to β-diketonato (1574 cm −1 ) was observed)
Elemental analysis (C 24 H 46 O 6 Si 2 Co); Carbon: 52.9%, hydrogen: 8.53%, cobalt: 10.7%
(Theoretical value: Carbon: 52.8%, Hydrogen: 8.50%, Cobalt: 10.8%)
参考例２（ビス（６−メチル−２−トリメチルシリルオキシ−３，５−ヘプタンジオナト）コバルト（ＩＩ）（以下、Ｃｏ（ｄｓｏｐｄ）２と称する）の合成）
攪拌装置、温度計及び滴下漏斗を備えた内容積２００ｍｌのフラスコに、酢酸コバルト（ＩＩ）・４水和物６.０１ｇ（２４.１ｍｍｏｌ）を水２０ｍｌに溶解させ、それにヘキサン４０ｍｌ、更に６−メチル−２−トリメチルシリルオキシ−３，５−ヘプタンジオン１１.２ｇ（４８.７ｍｍｏｌ）を添加した。室温下、１０分攪拌後、炭酸水素ナトリウム４．１ｇ（２４.４ｍｍｏｌ）を水５０ｍｌを溶解させた水溶液を室温下、滴下し、攪拌しながら室温で２０分間反応させた。反応終了後、有機層を分液した。該有機層を水で洗浄し、無水硫酸ナトリウムで乾燥させた。濾過後、濾液を濃縮して、濃縮物を減圧蒸留（１７０℃、１９Ｐａ）し、赤紫色粘性液体として、（ビス（６−メチル−２−トリメチルシリルオキシ−３，５−ヘプタンジオナト）コバルト（ＩＩ）４．２ｇを得た（単離収率；３４％）。
（ビス（６−メチル−２−トリメチルシリルオキシ−３，５−ヘプタンジオナト）コバルト（ＩＩ）は、以下の物性値で示される新規な化合物である。
Reference Example 2 (Synthesis of bis (6-methyl-2-trimethylsilyloxy-3,5-heptanedionato) cobalt (II) (hereinafter referred to as Co (dsopp) 2 ))
In a 200-ml flask equipped with a stirrer, thermometer and dropping funnel, 6.01 g (24.1 mmol) of cobalt (II) acetate tetrahydrate was dissolved in 20 ml of water, and 40 ml of hexane, Methyl-2-trimethylsilyloxy-3,5-heptanedione 11.2 g (48.7 mmol) was added. After stirring at room temperature for 10 minutes, an aqueous solution in which 50 g of water was dissolved in 4.1 g (24.4 mmol) of sodium bicarbonate was added dropwise at room temperature, and the mixture was reacted at room temperature for 20 minutes with stirring. After completion of the reaction, the organic layer was separated. The organic layer was washed with water and dried over anhydrous sodium sulfate. After filtration, the filtrate was concentrated, and the concentrate was distilled under reduced pressure (170 ° C., 19 Pa) to obtain (bis (6-methyl-2-trimethylsilyloxy-3,5-heptanedionate) cobalt (II) as a reddish purple viscous liquid. 4.2 g was obtained (isolated yield; 34%).
(Bis (6-methyl-2-trimethylsilyloxy-3,5-heptanedionato) cobalt (II) is a novel compound represented by the following physical property values.
ＩＲ（ｎｅａｔ（ｃｍ−１））；２９６５，１５８１，１５２７，１４３０，１２５２，１１２９，１０９３，１０４０，９７２，９０４，８６２，８４３
元素分析（Ｃ２２Ｈ４２Ｏ６Ｓｉ２Ｃｏ）；炭素：５１．２％，水素：８．１６％，コバルト：１１．３％
（理論値；炭素：５１.０％，水素：８．１８％，コバルト：１１．４％）
IR (neat (cm −1 )); 2965, 1581, 1527, 1430, 1252, 1129, 1093, 1040, 972, 904, 862, 843
Elemental analysis (C 22 H 42 O 6 Si 2 Co); Carbon: 51.2%, hydrogen: 8.16%, cobalt: 11.3%
(Theoretical value: Carbon: 51.0%, Hydrogen: 8.18%, Cobalt: 11.4%)
参考例３（ビス（２−メトキシ−６−メチル−３，５−ヘプタンジオナト）コバルト（ＩＩ）（以下、Ｃｏ（ｍｏｐｄ）２と称する）の合成）
攪拌装置、温度計及び滴下漏斗を備えた内容積１００ｍｌのフラスコに、２８％ナトリウムメトキシドのメタノール溶液４．３７ｇ（２２．７ｍｍｏｌ）を加え、氷冷下、２−メトキシ−６−メチル−３，５−ヘプタンジオン４．００ｇ（２３．２ｍｍｏｌ）をゆるやかに滴下し、５分間攪拌させた。次いで、塩化コバルト（ＩＩ）６水塩２．７０ｇ（１１．３ｍｍｏｌ）をメタノール２０ｍｌに溶解させた溶液をゆるやかに滴下し、氷冷下、攪拌しながら３０分間反応させた。反応終了後、反応液から減圧下でメタノールを留去した。その後、エーテル５０ｍｌ及び水３０ｍｌを加え、有機層を分液した後に、無水硫酸ナトリウムで乾燥させた。濾過後、濾液を濃縮した後、濃縮物を減圧蒸留（１７５℃、６７Ｐａ）し、粘性のある暗紫色液体として、ビス（２−メトキシ−６−メチル−３，５−ヘプタンジオナト）コバルト（ＩＩ）４．１７ｇを得た（単離収率；９２％）。
ビス（２−メトキシ−６−メチル−３，５−ヘプタンジオナト）コバルト（ＩＩ）は、以下の物性値で示される新規な化合物である。
Reference Example 3 (Synthesis of bis (2-methoxy-6-methyl-3,5-heptanedionato) cobalt (II) (hereinafter referred to as Co (mopd) 2 ))
To a 100-ml flask equipped with a stirrer, thermometer and dropping funnel was added 4.37 g (22.7 mmol) of 28% sodium methoxide in methanol, and 2-methoxy-6-methyl-3 under ice-cooling. , 5-Heptanedione 4.00 g (23.2 mmol) was slowly added dropwise and stirred for 5 minutes. Next, a solution prepared by dissolving 2.70 g (11.3 mmol) of cobalt (II) chloride hexahydrate in 20 ml of methanol was slowly added dropwise and reacted for 30 minutes with stirring under ice cooling. After completion of the reaction, methanol was distilled off from the reaction solution under reduced pressure. Thereafter, 50 ml of ether and 30 ml of water were added, and the organic layer was separated and dried over anhydrous sodium sulfate. After filtration, the filtrate was concentrated, and the concentrate was distilled under reduced pressure (175 ° C., 67 Pa) to give bis (2-methoxy-6-methyl-3,5-heptanedionato) cobalt (II) 4 as a viscous dark purple liquid. .17 g was obtained (isolation yield; 92%).
Bis (2-methoxy-6-methyl-3,5-heptanedionato) cobalt (II) is a novel compound represented by the following physical property values.
ＩＲ（ｎｅａｔ（ｃｍ−１））；３３９７（ｂｒ），２９７２，２９３２，１５９９，１５１１，１４３１，１３３３，１２１１，１１１７，１０５９，９１２，８０３，５６３（β−ジケトン特有のピーク（１６０７ｃｍ−１）が消失し、β−ジケトナト特有のピーク（１５９９ｃｍ−１）が観察された）
元素分析（Ｃ１８Ｈ３０Ｏ６Ｃｏ）；炭素：５３．８％，水素：７．５６％，コバルト：１４．６％
（理論値；炭素：５３．９％，水素：７．５３％，コバルト：１４．７％）
ＭＳ（ｍ／ｅ）；６３１、４０１、３５８、３４０、５９
ＭＳの結果より、このコバルト錯体は二量体構造であると推定される。
IR (neat (cm-1)); 3397 (br), 2972, 2932, 1599, 1511, 1431, 1333, 1211, 1117, 1059, 912, 803, 563 (β-diketone peculiar peak (1607 cm-1) Disappeared, and a peak (1599 cm −1 ) peculiar to β-diketonato was observed)
Elemental analysis (C 18 H 30 O 6 Co ); carbon: 53.8%, hydrogen: 7.56%, cobalt: 14.6%
(Theoretical value: Carbon: 53.9%, Hydrogen: 7.53%, Cobalt: 14.7%)
MS (m / e); 631, 401, 358, 340, 59
From the MS results, this cobalt complex is presumed to have a dimer structure.
実施例２〜３、比較例１〜２（蒸着実験；コバルト薄膜の製造）
実施例１で得られたコバルト錯体を用いて、ＣＶＤ法による蒸着実験を行い、成膜特性を評価した。
評価試験には、図１に示す装置を使用した。気化器３（ガラス製アンプル）にあるコバルト錯体２０は、ヒーター１０Ｂで加熱されて気化し、マスフローコントローラー１Ａを経て予熱器１０Ａで予熱後導入されたヘリウムガスに同伴し気化器３を出る。気化器３を出たガスは、マスフローコントローラー１Ｂ、ストップバルブ２を経て導入された水素ガスとともに反応器４に導入される。反応系内圧力は真空ポンプ手前のバルブ６の開閉により、所定圧力にコントロールされ、圧力計５によってモニターされる。ガラス製反応器の中央部はヒーター１０Ｃで加熱可能な構造となっている。反応器に導入されたコバルト錯体は、反応器内中央部にセットされ、ヒータ１０Ｃで所定の温度に加熱された被蒸着基板２１の表面上で還元熱分解し、基板２１上にコバルト薄膜が析出する。反応器４を出たガスは、トラップ７、真空ポンプを経て、大気中に排気される構造となっている。
Examples 2-3 and Comparative Examples 1-2 (deposition experiment; production of cobalt thin film)
Using the cobalt complex obtained in Example 1, a vapor deposition experiment by the CVD method was performed to evaluate the film formation characteristics.
The apparatus shown in FIG. 1 was used for the evaluation test. The cobalt complex 20 in the vaporizer 3 (glass ampule) is heated and vaporized by the heater 10B, and exits the vaporizer 3 along with the helium gas introduced after preheating by the preheater 10A via the mass flow controller 1A. The gas exiting the vaporizer 3 is introduced into the reactor 4 together with the hydrogen gas introduced through the mass flow controller 1B and the stop valve 2. The pressure in the reaction system is controlled to a predetermined pressure by opening and closing the valve 6 in front of the vacuum pump, and is monitored by the pressure gauge 5. The central part of the glass reactor has a structure that can be heated by the heater 10C. The cobalt complex introduced into the reactor is set at the center in the reactor and undergoes reductive pyrolysis on the surface of the deposition substrate 21 heated to a predetermined temperature by the heater 10C, and a cobalt thin film is deposited on the substrate 21. To do. The gas exiting the reactor 4 is exhausted to the atmosphere via a trap 7 and a vacuum pump.
蒸着条件及び蒸着結果（膜特性）を表１に示す。なお、被蒸着基盤としては、６ｍｍ×２０ｍｍサイズの矩形のものを使用した。 The deposition conditions and deposition results (film characteristics) are shown in Table 1. Note that a 6 mm × 20 mm rectangular substrate was used as the deposition base.
コバルト含有薄膜の製造に使用したコバルト錯体（実施例１及び参考例２〜３で合成）は以下の通りである。 The cobalt complex (synthesize | combined in Example 1 and Reference Examples 2-3) used for manufacture of a cobalt containing thin film is as follows.
該結果より、本発明のコバルト錯体が、優れた成膜性を有することが分かる。 From the results, it can be seen that the cobalt complex of the present invention has excellent film forming properties.
本発明は、化学気相蒸着法（ＣＶＤ法）によりコバルト原子を含有するコバルト薄膜を形成させる際に使用可能な、コバルト錯体に関する。本発明は、又、当該コバルト錯体を用いてコバルト含有薄膜を製造する方法に関する。 The present invention relates to a cobalt complex that can be used when forming a cobalt thin film containing cobalt atoms by chemical vapor deposition (CVD). The present invention also relates to a method for producing a cobalt-containing thin film using the cobalt complex.
３ 気化器
４ 反応器
１０Ｂ 気化器ヒータ
１０Ｃ 反応器ヒータ
２０ 原料コバルト錯体融液
２１ 基板
3 Vaporizer 4 Reactor 10B Vaporizer heater 10C Reactor heater 20 Raw material cobalt complex melt 21 Substrate
Claims (7)
で示されるβ-ジケトナト基を配位子として有するコバルト錯体。 Formula (I)
A cobalt complex having a β-diketonato group represented by
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009080801A JP2010229112A (en) | 2009-03-30 | 2009-03-30 | COBALT COMPLEX CONTAINING beta-DIKETONATO GROUP AS LIGAND AND METHOD FOR PRODUCING COBALT-CONTAINING THIN FILM USING THE SAME |
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| JP2009080801A JP2010229112A (en) | 2009-03-30 | 2009-03-30 | COBALT COMPLEX CONTAINING beta-DIKETONATO GROUP AS LIGAND AND METHOD FOR PRODUCING COBALT-CONTAINING THIN FILM USING THE SAME |
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