JP5454141B2 - Organic platinum complex and method for producing platinum-containing thin film by chemical vapor deposition using the platinum complex - Google Patents
Organic platinum complex and method for producing platinum-containing thin film by chemical vapor deposition using the platinum complex Download PDFInfo
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims description 164
- 229910052697 platinum Inorganic materials 0.000 title claims description 76
- 239000010409 thin film Substances 0.000 title claims description 37
- 238000004519 manufacturing process Methods 0.000 title claims description 24
- 238000005229 chemical vapour deposition Methods 0.000 title claims description 18
- 125000003545 alkoxy group Chemical group 0.000 claims description 22
- 125000004432 carbon atom Chemical group C* 0.000 claims description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 18
- 125000003342 alkenyl group Chemical group 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 7
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical group O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 6
- 229910001882 dioxygen Inorganic materials 0.000 claims description 6
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 3
- 125000005082 alkoxyalkenyl group Chemical group 0.000 claims description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 3
- 150000001721 carbon Chemical group 0.000 claims description 3
- 238000006467 substitution reaction Methods 0.000 claims description 3
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- -1 for example Substances 0.000 description 43
- 239000003446 ligand Substances 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 125000005595 acetylacetonate group Chemical group 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 6
- 239000010408 film Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- PRBHEGAFLDMLAL-UHFFFAOYSA-N 1,5-Hexadiene Natural products CC=CCC=C PRBHEGAFLDMLAL-UHFFFAOYSA-N 0.000 description 5
- RUGWMIIOLUFUAH-UHFFFAOYSA-N CCOC(CCC=C)C[Pt+] Chemical compound CCOC(CCC=C)C[Pt+] RUGWMIIOLUFUAH-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 238000000151 deposition Methods 0.000 description 5
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical compound C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 5
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000006200 vaporizer Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 4
- 239000012044 organic layer Substances 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 230000008016 vaporization Effects 0.000 description 4
- BLXIGQNPXUFMFP-UHFFFAOYSA-N COC(CCC=C)C[Pt+] Chemical compound COC(CCC=C)C[Pt+] BLXIGQNPXUFMFP-UHFFFAOYSA-N 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 3
- 125000003963 dichloro group Chemical group Cl* 0.000 description 3
- 150000001993 dienes Chemical class 0.000 description 3
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 239000011261 inert gas 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
- HRGDZIGMBDGFTC-UHFFFAOYSA-N platinum(2+) Chemical compound [Pt+2] HRGDZIGMBDGFTC-UHFFFAOYSA-N 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethylcyclohexane Chemical compound CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 150000003057 platinum Chemical class 0.000 description 2
- 150000003058 platinum compounds Chemical class 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- 125000006274 (C1-C3)alkoxy group Chemical group 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- 239000003708 ampul Substances 0.000 description 1
- 125000000522 cyclooctenyl group Chemical group C1(=CCCCCCC1)* 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 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
- 150000004687 hexahydrates Chemical class 0.000 description 1
- 125000006038 hexenyl group Chemical group 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- 239000012046 mixed solvent Substances 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
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- GYBMSOFSBPZKCX-UHFFFAOYSA-N sodium;ethanol;ethanolate Chemical compound [Na+].CCO.CC[O-] GYBMSOFSBPZKCX-UHFFFAOYSA-N 0.000 description 1
- SUBJHSREKVAVAR-UHFFFAOYSA-N sodium;methanol;methanolate Chemical compound [Na+].OC.[O-]C SUBJHSREKVAVAR-UHFFFAOYSA-N 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000001424 substituent group Chemical group 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
- 238000012546 transfer Methods 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0086—Platinum compounds
- C07F15/0093—Platinum compounds without a metal-carbon linkage
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
- C07C49/92—Ketonic chelates
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/06—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material
- C23C16/18—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material from metallo-organic compounds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Chemical Vapour Deposition (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
本発明は、新規な有機白金錯体、及び当該白金錯体を用いた化学気相蒸着法（Ｃｈｅｍｉｃａｌ Ｖａｐｏｒ Ｄｅｐｏｓｉｔｉｏｎ法；以下、ＣＶＤ法と称する）による白金含有薄膜の製造法に関する。 The present invention relates to a novel organic platinum complex and a method for producing a platinum-containing thin film by a chemical vapor deposition method (hereinafter referred to as a CVD method) using the platinum complex.
近年、ＤＲＡＭ、ＦｅＲＡＭ等のメモリデバイスの薄膜電極材料として、電気特性が優れている白金含有薄膜、好ましくは金属白金薄膜の使用が検討されている。これらの白金含有薄膜の製造法としては、例えば、均一な薄膜を製造し易いＣＶＤ法による成膜が最も盛んに採用されており、それに適した原料化合物が求められている。 In recent years, the use of platinum-containing thin films, preferably metallic platinum thin films, having excellent electrical characteristics, has been studied as thin film electrode materials for memory devices such as DRAM and FeRAM. As a method for producing these platinum-containing thin films, for example, film formation by the CVD method, which is easy to produce a uniform thin film, has been most widely adopted, and a raw material compound suitable for the film formation is required.
ところで、ＣＶＤ法による薄膜形成において使用される白金錯体としては、例えば、β−ジケトナト白金錯体やアルキル白金錯体が開示されている（例えば、非特許文献１、特許文献１参照）。しかしながら、例えば、β−ジケトナト配位子のみからなる白金錯体は一般的に高融点であり、またアルキル白金錯体は化学的、熱的に不安定であって、これまで提案されてきた白金錯体は必ずしも物性的に満足出来るものではなかった。 By the way, as a platinum complex used in thin film formation by CVD method, (beta) -diketonato platinum complex and alkyl platinum complex are disclosed, for example (for example, refer nonpatent literature 1 and patent document 1). However, for example, a platinum complex consisting only of a β-diketonato ligand generally has a high melting point, and an alkyl platinum complex is chemically and thermally unstable. It was not always satisfactory in terms of physical properties.
又、非特許文献２には、メトキシ基で置換されたシクロオクテニル基を配位子とするβ−ジケトナト白金錯体が開示されているが、ＣＶＤ法による白金含有薄膜の製造に関する記述は全くない。又、記載されている白金錯体は、室温で固体のため、ＣＶＤ法での使用には問題が懸念される。
本発明の課題は、即ち、上記問題点を解決し、低融点を有し、且つ水分、空気及び熱に対しての安定性に優れるとともに、ＣＶＤ法による白金含有薄膜、特には金属白金薄膜の製造に適した新規白金錯体を提供することにある。本発明の課題は、又、当該白金錯体を用いた、ＣＶＤ法による白金含有薄膜の製造法、特には金属白金薄膜の製造法を提供することにもある。 An object of the present invention is to solve the above problems, have a low melting point, and have excellent stability to moisture, air and heat, and a platinum-containing thin film by the CVD method, particularly a metal platinum thin film. The object is to provide a novel platinum complex suitable for production. The subject of this invention is also providing the manufacturing method of the platinum containing thin film by CVD method using the said platinum complex, especially the manufacturing method of a metal platinum thin film.
本発明は以下の事項に関する。 The present invention relates to the following matters.
１． 一般式（１） 1. General formula (1)
Ｚは、水素原子、あるいは炭素数１〜４の直鎖又は分枝状のアルキル基を示し、
Ｌは、アルコキシアルケニル基（アルコキシ基で置換された直鎖又は分枝状のアルケニル基）を示す。）
で示される有機白金錯体。
Z represents a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms,
L represents an alkoxyalkenyl group (a linear or branched alkenyl group substituted with an alkoxy group). )
An organic platinum complex represented by
２． Ｌ中のアルコキシ基の炭素数が１〜４である上記１記載の有機白金錯体。 2. 2. The organoplatinum complex according to 1 above, wherein the alkoxy group in L has 1 to 4 carbon atoms.
３． Ｌ中のアルケニル基の炭素数が４〜１０である上記１記載の有機白金錯体。 3. 2. The organoplatinum complex according to 1 above, wherein the alkenyl group in L has 4 to 10 carbon atoms.
４． 上記１記載の有機白金錯体を用いた、化学気相蒸着法による白金含有薄膜の製造法。 4). A method for producing a platinum-containing thin film by chemical vapor deposition using the organic platinum complex described in 1 above.
５． 有機白金錯体又は有機白金錯体の溶媒溶液を白金供給源として用いる上記４記載の白金含有薄膜の製造法。 5. 5. The method for producing a platinum-containing thin film according to 4 above, wherein an organic platinum complex or a solvent solution of the organic platinum complex is used as a platinum supply source.
６． さらに水素源を用いる上記５記載の白金含有薄膜の製造法。 6). 6. The method for producing a platinum-containing thin film as described in 5 above, further using a hydrogen source.
７． 水素源が水素ガスである上記６記載の白金含有薄膜の製造法。 7). 7. The method for producing a platinum-containing thin film according to 6 above, wherein the hydrogen source is hydrogen gas.
８． さらに酸素源を用いる上記５記載の白金含有薄膜の製造法。 8). 6. The method for producing a platinum-containing thin film according to 5 above, further using an oxygen source.
９． 酸素源が酸素ガスである上記８記載の白金含有薄膜の製造法。 9. 9. The method for producing a platinum-containing thin film according to 8 above, wherein the oxygen source is oxygen gas.
１０． 使用する溶媒が、脂肪族炭化水素類、芳香族炭化水素類及びエーテル類からなる群より選ばれる少なくとも１種の溶媒である上記５記載の白金含有薄膜の製造法。 10. 6. The method for producing a platinum-containing thin film according to 5 above, wherein the solvent used is at least one solvent selected from the group consisting of aliphatic hydrocarbons, aromatic hydrocarbons, and ethers.
本発明の前記一般式（１）で示される有機白金錯体は、融点が低く、水分、空気及び熱に対しての安定性にも優れており、ＣＶＤ法による白金含有薄膜の製造に適している。更に、この有機白金錯体を白金供給源として用いることにより、実質的に酸素原子を含まない金属白金膜をＣＶＤ法で製造することができる。 The organoplatinum complex represented by the general formula (1) of the present invention has a low melting point and excellent stability to moisture, air and heat, and is suitable for the production of a platinum-containing thin film by the CVD method. . Furthermore, by using this organic platinum complex as a platinum supply source, a metal platinum film substantially free of oxygen atoms can be produced by the CVD method.
１Ａ マスフローコントローラー
１Ｂ マスフローコントローラー
２ ストップバルブ
３ 気化器
４ 反応器
５ 圧力計
６ バルブ
７ トラップ
１０Ａ 予熱器
１０Ｂ 気化器ヒーター
１０Ｃ 反応器ヒーター
２０ 原料有機白金錯体融液
２１ 基板1A mass flow controller 1B mass flow controller 2
前記の一般式（１）において、Ｘ及びＹは、それぞれ独立に、アルコキシ基で置換されていても良い炭素数１〜８の直鎖又は分枝状のアルキル基を示す。Ｘ及びＹとしては、アルコキシ基で置換されていても良い炭素数１〜６のアルキル基が好ましく、アルコキシ基で置換されていても良い炭素数１〜３のアルキル基が特に好ましい。置換基であるアルコキシ基としては、炭素数１〜３のアルコキシ基が好ましく、メトキシ基、エトキシ基がより好ましく、メトキシ基が特に好ましい。 In the general formula (1), X and Y each independently represent a linear or branched alkyl group having 1 to 8 carbon atoms which may be substituted with an alkoxy group. X and Y are preferably an alkyl group having 1 to 6 carbon atoms which may be substituted with an alkoxy group, and particularly preferably an alkyl group having 1 to 3 carbon atoms which may be substituted with an alkoxy group. As an alkoxy group which is a substituent, a C1-C3 alkoxy group is preferable, a methoxy group and an ethoxy group are more preferable, and a methoxy group is especially preferable.
Ｘ及びＹとしては、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、ヘキシル基、ヘプチル基、オクチル基、１−メトキシエチル基、１−エトキシエチル基等が挙げられるが、好ましくはメチル基、エチル基、ｎ−プロピル基、イソプロピル基、１−メトキシエチル基であり、特に好ましくはメチル基である。また、Ｘがイソプロピル基であり、Ｙが１−メトキシエチル基であることも特に好ましい。 Examples of X and Y include, for example, 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, 1-methoxy group. Examples thereof include an ethyl group and a 1-ethoxyethyl group, preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and a 1-methoxyethyl group, and particularly preferably a methyl group. It is also particularly preferred that X is an isopropyl group and Y is a 1-methoxyethyl group.
Ｚは、水素原子、あるいは炭素数１〜４の直鎖又は分枝状のアルキル基を示す。 Z represents a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms.
Ｚとしては、例えば、水素原子、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−ブチル基等が挙げられるが、好ましくは水素原子、メチル基、エチル基であり、特に好ましくは水素原子である。 Examples of Z include a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a t-butyl group, and preferably a hydrogen atom, a methyl group, or an ethyl group. A group, particularly preferably a hydrogen atom.
β−ジケトナト配位子としては、Ｘ及びＹがメチル基であり、Ｚが水素原子であるもの、またはＸがイソプロピル基であり、Ｙが１−メトキシエチル基であり、Ｚが水素原子であるものが特に好ましく、Ｘ及びＹがメチル基であり、Ｚが水素原子であるものが更に好ましい。 As the β-diketonato ligand, X and Y are methyl groups and Z is a hydrogen atom, or X is an isopropyl group, Y is a 1-methoxyethyl group, and Z is a hydrogen atom Particularly preferred are those wherein X and Y are methyl groups, and Z is a hydrogen atom.
又、Ｌは、アルコキシアルケニル基、即ち、アルコキシ基で置換された直鎖又は分枝状のアルケニル基を示す。後述する式で示されるように、アルケニル基の炭素−炭素二重結合は、通常はＰｔに配位結合していると考えられる。 L represents an alkoxyalkenyl group, that is, a linear or branched alkenyl group substituted with an alkoxy group. As shown by the formula described below, the carbon-carbon double bond of the alkenyl group is usually considered to be coordinated to Pt.
Ｌ中のアルコキシ基としては、炭素数１〜４のものが好ましく、メトキシ基、エトキシ基、イソプロポキシ基がより好ましく、メトキシ基、エトキシ基が特に好ましい。 As an alkoxy group in L, a C1-C4 thing is preferable, a methoxy group, an ethoxy group, and an isopropoxy group are more preferable, and a methoxy group and an ethoxy group are especially preferable.
Ｌ中のアルケニル基としては、炭素数４〜１０のものが好ましく、炭素数４〜６のものがより好ましく、炭素数６のもの（ヘキセニル基）が特に好ましい。 The alkenyl group in L is preferably one having 4 to 10 carbon atoms, more preferably one having 4 to 6 carbon atoms, and particularly preferably one having 6 carbon atoms (hexenyl group).
アルコキシ基の置換位置は、特に限定されないが、Ｐｔに結合する炭素原子を１位としたときに、２位であることが好ましい。なお、アルケニル基が分枝状である場合も、アルコキシ基の置換位置は特に限定されず、いずれの炭素原子にアルコキシ基が結合していてもよい。 The substitution position of the alkoxy group is not particularly limited, but is preferably the 2-position when the carbon atom bonded to Pt is the 1-position. Even when the alkenyl group is branched, the substitution position of the alkoxy group is not particularly limited, and the alkoxy group may be bonded to any carbon atom.
Ｌとしては、下記一般式（１−１）〜（１−３）で示されるものが好ましく、中でも、下記一般式（１−１）で示されるものが特に好ましい。 As L, those represented by the following general formulas (1-1) to (1-3) are preferable, and those represented by the following general formula (1-1) are particularly preferable.
Ｒａは、炭素数２〜４の直鎖アルケニル基を示し、
Ｒｂは、メチル基又はエチル基を示す。）
Ra represents a linear alkenyl group having 2 to 4 carbon atoms,
Rb represents a methyl group or an ethyl group. )
Ｌとしては、例えば、２−メトキシ−５−ヘキセニル基、２−メトキシ−４−ペンテニル基、２−メトキシ−３−ブテニル基、２−エトキシ−５−ヘキセニル基、２−エトキシ−４−ペンテニル基、２−エトキシ−３−ブテニル基、２−ブトキシ−５−ヘキセニル基、２−ブトキシ−４−ペンテニル基、２−ブトキシ−３−ブテニル基、１−メチル−２−メトキシ−３−ペンテニル基、１−メチル−２−エトキシ−３−ペンテニル基、２−イソプロポキシ−５−ヘキセニル基、２−イソプロポキシ−４−ペンテニル基、２−イソプロポキシ−３−ブテニル基、１−メトキシメチル−４−ペンテニル基、１−エトキシメチル−４−ペンテニル基等が挙げられるが、好ましくは２−メトキシ−５−ヘキセニル基、２−メトキシ−４−ペンテニル基、２−エトキシ−５−ヘキセニル基、２−エトキシ−４−ペンテニル基、２−イソプロポキシ−５−ヘキセニル基、２−イソプロポキシ−４−ペンテニル基、１−エトキシメチル−４−ペンテニル基であり、特に好ましくは２−メトキシ−５−ヘキセニル基、２−エトキシ−５−ヘキセニル基、２−イソプロポキシ−５−ヘキセニル基、１−エトキシメチル−４−ペンテニル基であり、更に好ましくは２−メトキシ−５−ヘキセニル基、２−エトキシ−５−ヘキセニル基、１−エトキシメチル−４−ペンテニル基である。 As L, for example, 2-methoxy-5-hexenyl group, 2-methoxy-4-pentenyl group, 2-methoxy-3-butenyl group, 2-ethoxy-5-hexenyl group, 2-ethoxy-4-pentenyl group 2-ethoxy-3-butenyl group, 2-butoxy-5-hexenyl group, 2-butoxy-4-pentenyl group, 2-butoxy-3-butenyl group, 1-methyl-2-methoxy-3-pentenyl group, 1-methyl-2-ethoxy-3-pentenyl group, 2-isopropoxy-5-hexenyl group, 2-isopropoxy-4-pentenyl group, 2-isopropoxy-3-butenyl group, 1-methoxymethyl-4- Pentenyl group, 1-ethoxymethyl-4-pentenyl group and the like can be mentioned, but preferably 2-methoxy-5-hexenyl group, 2-methoxy-4-pentenyl group 2-ethoxy-5-hexenyl group, 2-ethoxy-4-pentenyl group, 2-isopropoxy-5-hexenyl group, 2-isopropoxy-4-pentenyl group, 1-ethoxymethyl-4-pentenyl group, Particularly preferred are 2-methoxy-5-hexenyl group, 2-ethoxy-5-hexenyl group, 2-isopropoxy-5-hexenyl group, 1-ethoxymethyl-4-pentenyl group, and more preferred is 2-methoxy- 5-hexenyl group, 2-ethoxy-5-hexenyl group, 1-ethoxymethyl-4-pentenyl group.
本発明の一般式（１）の有機白金錯体の具体的な化合物の例としては、下記式（２）〜（３３）に示される。 Examples of specific compounds of the organic platinum complex of the general formula (1) of the present invention are represented by the following formulas (2) to (33).
中でも、ＣＶＤ用原料化合物としては、上記式（２）〜（５）、（２２）〜（２５）、（２６）〜（２７）で示される有機白金錯体が好ましく、上記式（２）〜（４）、（２６）〜（２７）で示される有機白金錯体がより好ましく、上記式（２）〜（３）、（２６）〜（２７）で示される有機白金錯体が特に好ましい。 Especially, as a raw material compound for CVD, the organic platinum complex shown by said formula (2)-(5), (22)-(25), (26)-(27) is preferable, and said formula (2)-( 4) The organic platinum complexes represented by (26) to (27) are more preferred, and the organic platinum complexes represented by the above formulas (2) to (3) and (26) to (27) are particularly preferred.
本発明の前記一般式（１）で示される有機白金錯体は、例えば、水または有機溶媒中で、ハロゲン化白金酸、例えばヘキサクロロ白金酸などの白金化合物と、配位子（配位子Ｌ中のアルケニル基）となるジエン化合物とを反応させて、ジエン配位子を１個有する白金錯体（ジエン錯体）を合成した後、これを単離し、次いで、有機溶媒中で、得られたジエン錯体と、配位子Ｌ中のアルコキシ基となるアルコキシ基を含む金属アルコキシドと、配位子となるβ−ジケトン化合物とを反応させて、本発明の有機白金錯体を合成した後、これを単離することにより得ることができる。また、本発明の有機白金錯体は、水または水−有機溶媒混合溶媒中で、ハロゲン化白金酸塩、例えばテトラクロロ白金（ＩＩ）酸カリウムなどの白金化合物と、配位子（配位子Ｌ中のアルケニル基）となるジエン化合物とを反応させた後、溶媒を除去し、次いで、これに有機溶媒を加え、配位子Ｌ中のアルコキシ基となるアルコキシ基を含む金属アルコキシドを加えて反応させ、その後、配位子となるβ−ジケトン化合物を加えて反応させて、本発明の有機白金錯体を合成した後、これを単離することによっても得ることができる。 The organoplatinum complex represented by the general formula (1) of the present invention includes, for example, a platinum compound such as a halogenated platinic acid, for example, hexachloroplatinic acid, and a ligand (in the ligand L) in water or an organic solvent. The platinum complex (diene complex) having one diene ligand is synthesized by reacting with a diene compound that becomes an alkenyl group of the above-mentioned alkenyl group, and then isolated, and then the obtained diene complex in an organic solvent And a metal alkoxide containing an alkoxy group that becomes an alkoxy group in the ligand L and a β-diketone compound that becomes a ligand to synthesize the organoplatinum complex of the present invention, which is then isolated. Can be obtained. Further, the organic platinum complex of the present invention comprises a platinum compound such as a halogenated platinate, for example, potassium tetrachloroplatinate (II), and a ligand (ligand L) in water or a water-organic solvent mixed solvent. After the reaction with the diene compound to be an alkenyl group in the solvent, the solvent is removed, and then an organic solvent is added thereto, and a metal alkoxide containing an alkoxy group to be an alkoxy group in the ligand L is added to react. Then, a β-diketone compound as a ligand is added and reacted to synthesize the organoplatinum complex of the present invention, and then it can be isolated.
本発明のＣＶＤ法においては、薄膜形成のために有機白金錯体を気化させる必要があるが、本発明の有機白金錯体を気化させる方法としては、例えば、有機白金錯体自体を気化室に充填又は搬送して気化させる方法だけでなく、有機白金錯体を適当な溶媒（例えば、ヘキサン、メチルシクロヘキサン、エチルシクロヘキサン、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 of the present invention, it is necessary to vaporize the organic platinum complex in order to form a thin film. As a method of vaporizing the organic platinum complex of the present invention, for example, the organic platinum complex itself is filled or transported into the vaporization chamber. In addition to the method of vaporizing, an organic platinum complex is converted into an appropriate solvent (for example, aliphatic hydrocarbons such as hexane, methylcyclohexane, ethylcyclohexane, and octane; aromatic hydrocarbons such as toluene; tetrahydrofuran, dibutyl ether, etc. The method can be used in which the solution diluted in (1) is introduced into the vaporizing chamber by a liquid transfer pump and vaporized (solution method).
基板上への金属の蒸着方法としては、公知のＣＶＤ法で行うことが出来、例えば、常圧又は減圧下にて、当該有機白金錯体を水素源（例えば、水素ガス等の還元性ガスやアルコール類）や酸素源（例えば酸素ガス）、又は不活性ガスとともに加熱した基板上に送り込んで白金含有薄膜を蒸着させる方法が使用出来る。又、プラズマＣＶＤ法で白金含有薄膜を蒸着させる方法も使用出来る。なお、水素等の水素源となるガスや、酸素等の酸素源となるガスは、不活性ガスで希釈されていても良い。 The metal can be deposited on the substrate by a known CVD method. For example, the organic platinum complex can be converted into a hydrogen source (for example, a reducing gas such as hydrogen gas or alcohol under normal pressure or reduced pressure). ), An oxygen source (for example, oxygen gas), or a method in which a platinum-containing thin film is deposited by feeding it onto a substrate heated with an inert gas. Moreover, the method of vapor-depositing a platinum containing thin film by plasma CVD method can also be used. Note that a gas serving as a hydrogen source such as hydrogen and a gas serving as an oxygen source such as oxygen may be diluted with an inert gas.
当該有機白金錯体と、水素源、酸素源又は不活性ガスを用いて白金含有薄膜を蒸着させる際、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（基板温度）は、好ましくは５０〜５００℃、更に好ましくは１００〜４００℃である。又、水素ガス又は酸素ガスにより金属薄膜を蒸着させる際の全ガス量に対する水素ガス又は酸素ガスの含有割合は、好ましくは０．０１〜９５容量％、更に好ましくは０．１〜９０容量％である。 When the platinum-containing thin film is deposited using the organic platinum complex and a hydrogen source, an oxygen source or an inert gas, the pressure in the reaction system is preferably 1 Pa to 200 kPa, more preferably 10 Pa to 110 kPa. The temperature of the object (substrate temperature) is preferably 50 to 500 ° C, more preferably 100 to 400 ° C. The content ratio of the hydrogen gas or oxygen gas to the total gas amount when the metal thin film is deposited by hydrogen gas or oxygen gas is preferably 0.01 to 95% by volume, more preferably 0.1 to 90% by volume. is there.
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〔ジクロロ（１，５−ヘキサジエン）白金（ＩＩ）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、ヘキサクロロ白金酸六水和物３．９７ｇ（７．６６ｍｍｏｌ）を入れ、減圧下、６５℃で１時間乾燥した。その後、室温まで冷却した後に酢酸１８ｍｌを加えた。次いで、６５℃まで加熱して１，５−ヘキサジエン４．１５ｇ（５０．５ｍｍｏｌ）を滴下し、攪拌しながら同温度で１０時間反応させた。反応終了後、反応液を室温まで冷却し、塩化メチレン３５ｍｌ及び水５０ｍｌを加え、有機層を分液した後に濃縮した。得られた濃縮液にヘキサン１００ｍｌを加えて白色固体を沈殿させた。濾過後、濾物をヘキサンで洗浄し、室温にて減圧下で乾燥させ、白色固体として、ジクロロ（１，５−ヘキサジエン）白金（ＩＩ）２．１２ｇを得た（単離収率；８０％）。Reference Example 1 [Synthesis of dichloro (1,5-hexadiene) platinum (II)]
3.97 g (7.66 mmol) of hexachloroplatinic acid hexahydrate was placed in a flask having an internal volume of 100 ml equipped with a stirrer, a thermometer and a dropping funnel, and dried at 65 ° C. for 1 hour under reduced pressure. Then, after cooling to room temperature, 18 ml of acetic acid was added. Subsequently, it heated to 65 degreeC and 4.15 g (50.5 mmol) of 1, 5-hexadiene was dripped, and it was made to react at the same temperature for 10 hours, stirring. After completion of the reaction, the reaction solution was cooled to room temperature, 35 ml of methylene chloride and 50 ml of water were added, and the organic layer was separated and concentrated. 100 ml of hexane was added to the obtained concentrated liquid to precipitate a white solid. After filtration, the residue was washed with hexane and dried under reduced pressure at room temperature to obtain 2.12 g of dichloro (1,5-hexadiene) platinum (II) as a white solid (isolated yield; 80% ).
なお、ジクロロ（１，５−ヘキサジエン）白金（ＩＩ）は、物性値は以下の通りであった。 The physical properties of dichloro (1,5-hexadiene) platinum (II) were as follows.
ＩＲ（ｎｅａｔ（ｃｍ−１））；３０７０、３０１６、２９６４、２９４１、１５１１、１４５７、１４２５、１４０２、１３０６、１１１５、１００９、９４１、８６２、７７６、５９５、５０８
１Ｈ−ＮＭＲ（ＣＤＣｌ３，δ（ｐｐｍ））；２．２９〜２．４１（２Ｈ，ｍ）、２．６８−２．８０（２Ｈ，ｍ）、４．０４〜４．２８（２Ｈ，ｍ）、４．５０−５．２４（２Ｈ，ｍ）、５．６７〜５．７８（２Ｈ，ｍ）
ＭＳ（ｍ／ｅ）；３４８、３１２、２７４、２３３、６７、４１IR (neat (cm −1 )); 3070, 3016, 2964, 2941, 1511, 1457, 1425, 1402, 1306, 1115, 1009, 941, 862, 776, 595, 508
1 H-NMR (CDCl 3 , δ (ppm)); 2.29 to 2.41 (2H, m), 2.68-2.80 (2H, m), 4.04 to 4.28 (2H, m), 4.50-5.24 (2H, m), 5.67-5.78 (2H, m)
MS (m / e); 348, 312, 274, 233, 67, 41
実施例１〔（アセチルアセトナト）（２−メトキシ−５−ヘキセニル）白金（ＩＩ）（式（２）の化合物；以下、［Ｐｔ（ａｃａｃ）（ｍｏｈ）］と称する）の合成、出発原料；ジクロロ（１，５−ヘキサジエン）白金（ＩＩ）〕
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メタノール溶液３．５３ｇ（１８．３ｍｍｏｌ）を加え、水冷下、ジクロロ（１，５−ヘキサジエン）白金（ＩＩ）１．５６ｇ（４．４９ｍｍｏｌ）を塩化メチレン１５ｍｌに溶解させた溶液を滴下した。次いで、アセチルアセトン２．１０ｇ（２１．０ｍｍｏｌ）を加え、攪拌しながら同温度で１時間反応させた。反応終了後、反応液から有機層を分液し、水で洗浄した後に、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、濃縮物を減圧下で蒸留（１４０℃、４７Ｐａ）し、淡黄色粘性液体として、（アセチルアセトナト）（２−メトキシ−５−ヘキセニル）白金（ＩＩ）１．７０ｇを得た（単離収率；９３％）。この淡黄色粘性液体は、時間経過とともに白色固体（融点；８８〜９１℃）となった。Example 1 Synthesis of [(acetylacetonato) (2-methoxy-5-hexenyl) platinum (II) (compound of formula (2); hereinafter referred to as [Pt (acac) (moh)]), starting material; Dichloro (1,5-hexadiene) platinum (II)]
To a 100 ml flask equipped with a stirrer, thermometer and dropping funnel, 3.53 g (18.3 mmol) of 28% sodium methoxide methanol solution was added, and dichloro (1,5-hexadiene) platinum (II) was cooled with water. ) A solution prepared by dissolving 1.56 g (4.49 mmol) in 15 ml of methylene chloride was added dropwise. Next, 2.10 g (21.0 mmol) of acetylacetone was added and reacted at the same temperature for 1 hour with stirring. After completion of the reaction, the organic layer was separated from the reaction solution, washed with water, and dried over anhydrous sodium sulfate. After filtration, the filtrate was concentrated, and the concentrate was distilled under reduced pressure (140 ° C., 47 Pa) to give (acetylacetonato) (2-methoxy-5-hexenyl) platinum (II) as a pale yellow viscous liquid. 70 g was obtained (isolation yield; 93%). The pale yellow viscous liquid became a white solid (melting point: 88-91 ° C.) with time.
なお、（アセチルアセトナト）（２−メトキシ−５−ヘキセニル）白金（ＩＩ）は、以下の物性値で示される新規な化合物である。 In addition, (acetylacetonato) (2-methoxy-5-hexenyl) platinum (II) is a novel compound represented by the following physical property values.
ＩＲ（ｎｅａｔ（ｃｍ−１））；２９２８、２８７４、２８２０、１５８４、１５１５、１３８６、１２６３、１１３４、１０８０、９４９、９０３、７７５、６１８、４５１
（β−ジケトン特有のピーク（１６２２ｃｍ−１）が消失し、β−ジケトナト特有のピーク（１５８４ｃｍ−１）が観察された）
元素分析（Ｃ１２Ｈ２０Ｏ３Ｐｔ）；炭素：３５．５％、水素：４．９８％、白金：４７．９％
（理論値；炭素：３５．３８％、水素：４．９５％、白金：４７．８９％）
ＭＳ（ｍ／ｅ）；４０７、３７５、３０７、２７５、２３５、４３IR (neat (cm −1 )); 2928, 2874, 2820, 1584, 1515, 1386, 1263, 1134, 1080, 949, 903, 775, 618, 451
(A peak peculiar to β-diketone (1622 cm −1 ) disappeared, and a peak peculiar to β-diketonato (1584 cm −1 ) was observed)
Elemental analysis (C 12 H 20 O 3 Pt ); Carbon: 35.5%, hydrogen: 4.98% platinum: 47.9%
(Theoretical value: carbon: 35.38%, hydrogen: 4.95%, platinum: 47.89%)
MS (m / e); 407, 375, 307, 275, 235, 43
実施例２−１〔（アセチルアセトナト）（２−エトキシ−５−ヘキセニル）白金（ＩＩ）（式（３）の化合物；以下、［Ｐｔ（ａｃａｃ）（ｅｏｈ）］と称する）の合成、出発原料；ジクロロ（１，５−ヘキサジエン）白金（ＩＩ）〕
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、ナトリウムエトキシド３．５３ｇ（１８．３ｍｍｏｌ）及びエタノール８ｍｌを加え、水冷下、ジクロロ（１，５−ヘキサジエン）白金（ＩＩ）１．６２ｇ（４．６６ｍｍｏｌ）を塩化メチレン１２ｍｌに溶解させた溶液を滴下した。次いで、アセチルアセトン３．００ｇ（３０．０ｍｍｏｌ）を加え、攪拌しながら同温度で１時間反応させた。反応終了後、反応液から有機層を分液し、水で洗浄した後に、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、濃縮物を減圧下で蒸留（１４０℃、３３Ｐａ）し、淡黄色粘性液体として、（アセチルアセトナト）（２−エトキシ−５−ヘキセニル）白金（ＩＩ）１．７１ｇを得た（単離収率；８７％）。Example 2-1 Synthesis and start of [(acetylacetonato) (2-ethoxy-5-hexenyl) platinum (II) (compound of formula (3); hereinafter referred to as [Pt (acac) (eoh)]) Raw material; dichloro (1,5-hexadiene) platinum (II)]
Sodium ethoxide (3.53 g, 18.3 mmol) and ethanol (8 ml) were added to a 100 ml flask equipped with a stirrer, thermometer and dropping funnel, and dichloro (1,5-hexadiene) platinum (II) was added with water cooling. A solution prepared by dissolving 1.62 g (4.66 mmol) in 12 ml of methylene chloride was added dropwise. Next, 3.00 g (30.0 mmol) of acetylacetone was added, and the mixture was reacted at the same temperature for 1 hour with stirring. After completion of the reaction, the organic layer was separated from the reaction solution, washed with water, and dried over anhydrous sodium sulfate. After filtration, the filtrate was concentrated, and the concentrate was distilled under reduced pressure (140 ° C., 33 Pa) to give (acetylacetonato) (2-ethoxy-5-hexenyl) platinum (II) as a pale yellow viscous liquid. 71 g were obtained (isolation yield; 87%).
なお、（アセチルアセトナト）（２−エトキシ−５−ヘキセニル）白金（ＩＩ）は、以下の物性値で示される新規な化合物である。 In addition, (acetylacetonato) (2-ethoxy-5-hexenyl) platinum (II) is a novel compound represented by the following physical property values.
ＩＲ（ｎｅａｔ（ｃｍ−１））；２９７１、２９２６、１５８３、１５１６、１３８９、１２６５、１０８３、７８０、６１４、４４７
（β−ジケトン特有のピーク（１６２２ｃｍ−１）が消失し、β−ジケトナト特有のピーク（１５８３ｃｍ−１）が観察された）
元素分析（Ｃ１３Ｈ２２Ｏ３Ｐｔ）；炭素：３７．１％、水素：５．３０％、白金：４６．３％
（理論値；炭素：３７．０５％、水素：５．２６％、白金：４６．２９％）
ＭＳ（ｍ／ｅ）；４２１、３７６、３２１、２７６、２３５、４３IR (neat (cm −1 )); 2971, 2926, 1583, 1516, 1389, 1265, 1083, 780, 614, 447
(A peak peculiar to β-diketone (1622 cm −1 ) disappeared and a peak peculiar to β-diketonato (1583 cm −1 ) was observed)
Elemental analysis (C 13 H 22 O 3 Pt ); Carbon: 37.1%, hydrogen: 5.30% platinum: 46.3%
(Theoretical value: carbon: 37.05%, hydrogen: 5.26%, platinum: 46.29%)
MS (m / e); 421, 376, 321, 276, 235, 43
実施例２−２〔（アセチルアセトナト）（２−エトキシ−５−ヘキセニル）白金（ＩＩ）（式（３）の化合物；以下、［Ｐｔ（ａｃａｃ）（ｅｏｈ）］と称する）の合成、出発原料；テトラクロロ白金（ＩＩ）酸カリウム〕
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、テトラクロロ白金（ＩＩ）酸カリウム５．５５ｇ（１３．４ｍｍｏｌ）を入れ、それに水２０ｍｌ及び酢酸１０ｍｌを加え、更に１，５−ヘキサジエン１１．７ｇ（１４３ｍｍｏｌ）を加えて、６０℃で６時間攪拌した。得られた懸濁液を室温下で一晩放置した後、懸濁液を濃縮して淡黄色固体を得た。得られた固体にエタノール２５ｍｌを加えて、攪拌しながら１０℃で２０％ナトリウムエトキシドエタノール溶液１３．６５ｇ（５９．３ｍｍｏｌ）を滴下した。滴下後、１０℃で２時間攪拌して淡黄色の懸濁液を得た。得られた懸濁液にアセチルアセトン５．３５ｇ（５３．４ｍｍｏｌ）を滴下し、攪拌しながら同温度で１時間反応させた。反応終了後、反応液を濃縮して黄色のスラリーを得た。そのスラリーにメチルシクロヘキサン及び水を添加した後、有機層を分液し、水で洗浄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、濃縮物を減圧下で蒸留（１４０℃、１１Ｐａ）し、淡黄色粘性液体として、（アセチルアセトナト）（２−エトキシ−５−ヘキセニル）白金（ＩＩ）４．６５ｇを得た（単離収率；８２％）。Example 2-2 Synthesis of [(acetylacetonato) (2-ethoxy-5-hexenyl) platinum (II) (compound of formula (3); hereinafter referred to as [Pt (acac) (eoh)]), starting Raw material: Potassium tetrachloroplatinate (II)]
To a 100 ml flask equipped with a stirrer, a thermometer and a dropping funnel, 5.55 g (13.4 mmol) of potassium tetrachloroplatinate (II) was added, 20 ml of water and 10 ml of acetic acid were added, and 1,5 -Hexadiene 11.7g (143 mmol) was added and it stirred at 60 degreeC for 6 hours. The resulting suspension was allowed to stand overnight at room temperature, and then the suspension was concentrated to give a pale yellow solid. 25 ml of ethanol was added to the obtained solid, and 13.65 g (59.3 mmol) of a 20% sodium ethoxide ethanol solution was added dropwise at 10 ° C. with stirring. After dropping, the mixture was stirred at 10 ° C. for 2 hours to obtain a pale yellow suspension. To the resulting suspension, 5.35 g (53.4 mmol) of acetylacetone was added dropwise and reacted at the same temperature for 1 hour with stirring. After completion of the reaction, the reaction solution was concentrated to obtain a yellow slurry. After adding methylcyclohexane and water to the slurry, the organic layer was separated, washed with water, and dried over anhydrous sodium sulfate. After filtration, the filtrate was concentrated, and the concentrate was distilled (140 ° C., 11 Pa) under reduced pressure to give 4.65 g of (acetylacetonato) (2-ethoxy-5-hexenyl) platinum (II) as a pale yellow viscous liquid. (Isolated yield; 82%).
実施例３〜６（蒸着実験；金属白金薄膜の製造）
実施例１及び２−１で得られた有機白金錯体（［Ｐｔ（ａｃａｃ）（ｍｏｈ）］及び［Ｐｔ（ａｃａｃ）（ｅｏｈ）］）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。Examples 3 to 6 (deposition experiment; production of metal platinum thin film)
Using the organoplatinum complexes obtained in Examples 1 and 2-1 ([Pt (acac) (moh)] and [Pt (acac) (eoh)])), a vapor deposition experiment by a CVD method was performed, and film formation characteristics were obtained. Evaluated.
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）にある有機白金錯体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あるいは酸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白金錯体は、反応器内中央部にセットされ、ヒーター１０Ｃで所定の温度に加熱された被蒸着基板２１の表面上で反応し、基板２１上に金属白金薄膜が析出する。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。
The apparatus shown in FIG. 1 was used for the evaluation test. The
蒸着条件及び蒸着結果（膜特性）を表１に示す。なお、被蒸着基板としては、７ｍｍ×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. In addition, as a to-be-deposited board | substrate, the rectangular thing of 7 mm x 20 mm size was used.
該結果より、当該有機白金錯体（［Ｐｔ（ａｃａｃ）（ｍｏｈ）］及び［Ｐｔ（ａｃａｃ）（ｅｏｈ）］）が、低温で優れた成膜特性を有することが分かる。 The results show that the organoplatinum complexes ([Pt (acac) (moh)] and [Pt (acac) (eoh)]) have excellent film forming properties at low temperatures.
本発明によれば、低融点を有し、且つ水分、空気及び熱に対しての安定性に優れるとともに、ＣＶＤ法による白金含有薄膜の製造に適した新規有機白金錯体、及び当該有機白金錯体を用いたＣＶＤ法による金属白金含有薄膜の製造法を提供することができる。 According to the present invention, a novel organic platinum complex having a low melting point and excellent stability to moisture, air and heat, and suitable for producing a platinum-containing thin film by a CVD method, and the organic platinum complex The manufacturing method of the metal platinum containing thin film by the used CVD method can be provided.
Claims (9)
Ｚは、水素原子、あるいは炭素数１〜４の直鎖又は分枝状のアルキル基を示し、
Ｌは、アルコキシアルケニル基（アルコキシ基で置換された直鎖又は分枝状のアルケニル基）を示す。）
で示され、
前記Ｌは、炭素数１〜４のアルコキシ基で置換された炭素数４〜１０の直鎖又は分枝状のアルケニル基であり、アルコキシ基の置換位置は、Ｐｔに結合する炭素原子を１位としたときに２位であり、且つ、アルケニル基の炭素−炭素二重結合がＰｔに配位結合していることを特徴とする有機白金錯体。 General formula (1)
Z represents a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms,
L represents an alkoxyalkenyl group (a linear or branched alkenyl group substituted with an alkoxy group). )
In is shown,
L is a linear or branched alkenyl group having 4 to 10 carbon atoms substituted by an alkoxy group having 1 to 4 carbon atoms, and the substitution position of the alkoxy group is the 1st position of the carbon atom bonded to Pt. An organic platinum complex characterized in that it is in the 2-position and the carbon-carbon double bond of the alkenyl group is coordinated to Pt .
Ｒａは、炭素数２〜４の直鎖アルケニル基を示し、
Ｒｂは、メチル基又はエチル基を示す。） The organoplatinum complex according to claim 1 , wherein the L is represented by any one of the following general formulas (1-1) to (1-3) .
Ra represents a linear alkenyl group having 2 to 4 carbon atoms,
Rb represents a methyl group or an ethyl group. )
The method for producing a platinum-containing thin film according to claim 4 , wherein the solvent used is at least one solvent selected from the group consisting of aliphatic hydrocarbons, aromatic hydrocarbons and ethers.
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