JP4622098B2 - Stabilized silicon-containing alkene copper complex and method for producing the same - Google Patents

Description

（式中、Ｒ¹，Ｒ²は、炭素数１〜２０の弗化炭化水素基又は炭素数１〜２０の炭化水素基であり、Ｒ¹，Ｒ²の少なくとも一方は弗化炭化水素基である。Ｒ³は、水素原子、弗素原子、又は炭素数１〜２０の弗化炭化水素基を表わす。Ｒ⁴，Ｒ⁵，Ｒ⁶は、炭素数１〜２０の炭化水素基であり、少なくとも一つはＳｉに直結する三級炭化水素を有する炭化水素基を表わし、ｎは０〜２０の整数を表わす。）で示される珪素含有アルケン銅錯体及びその製造方法に関するものである。
【００１５】
以下、本発明について詳細に説明する。
【００１６】
上記一般式（１）おいて、Ｒ¹，Ｒ²は、炭素数１〜２０の弗化炭化水素基又は炭素数１〜２０の炭化水素基であり、Ｒ¹，Ｒ²の少なくとも一方は弗化炭化水素基である。炭素数が２０を越える場合は、原料の調達の困難さ及び純度の高いものの調達の困難さから好ましくない。
【００１７】
弗化炭化水素基としては、少なくとも一つ以上の弗素原子を有する炭化水素基であれば特に限定されるものではなく、弗化飽和炭化水素基又は弗化不飽和炭化水素基が挙げられる。
【００１８】
弗化飽和炭化水素基としては、例えば、トリフルオロメチル基、パーフルオロエチル基、パーフルオロプロピル基、パーフルオロシクロプロピル基、パーフルオロメチルシクロプロピル基、パーフルオロブチル基、パーフルオロシクロブチル基、パーフルオロペンチル基、パーフルオロシクロペンチル基、パーフルオロメチルシクロペンチル基、パーフルオロヘキシル基、パーフルオロシクロヘキシル基、パーフルオロ−１，２−ジメチルシクロヘキシル基、パーフルオロヘプチル基等のパーフルオロカーボン残基、フルオロメチル基、ジフルオロメチル基、１，１，１−トリフルオロエチル基、２−パーフルオロアルキルエチル基等のフルオロハイドロカーボン残基等を挙げることができる。
【００１９】
更に弗化不飽和炭化水素基として、例えば、パーフルオロエテニル基、パーフルオロプロペニル基、パーフルオロ−１，３−ブタジエニル基、シクロブテニル基、パーフルオロ−２−ブチニル基、ペンタフルオロフェニル基、パーフルオロトルイル基、ビス（トリフルオロメチル）フェニル基、パーフルオロナフタレニル基、パーフルオロインデニル基、パーフルオロフルオレニル基等を挙げることができる。
【００２０】
炭化水素基としては、炭素数１〜２０炭化水素基であり、好ましくは炭素数１〜１０であるアルキル基，アリール基，アリールアルキル基，アルキルアリール基を挙げることができる。具体的には、例えば、メチル基，エチル基，ｎ−プロピル基，ｉ−プロピル基，ｎ−ブチル基，ｉ−ブチル基，ｓｅｃ−ブチル基，ｔｅｒｔ．−ブチル基，ｎ−ペンチル基，ｔｅｒｔ．−アミル基，ｎ−ヘキシル基，シクロヘキシル基，フェニル基，トルイル基等を挙げることができる。
【００２１】
Ｒ¹，Ｒ²が共に弗化炭化水素基である場合、Ｒ¹，Ｒ²は、同一であっても異なっても良い。
【００２２】
Ｒ³は、Ｒ¹，Ｒ²と同様の炭素数１〜２０の弗化炭化水素基好ましくは銅錯体の蒸気圧を上昇させるために炭素数１〜１０の弗化炭化水素基、又は水素原子、弗素原子を示す。炭素数が２０を越える場合は、原料の調達の困難さ及び純度の高いものの調達の困難さから好ましくない。
【００２３】
Ｒ⁴，Ｒ⁵，Ｒ⁶は、炭素数１〜２０の炭化水素基であり、少なくとも一つは、Ｓｉに直結する三級炭素を有する炭化水素基である。炭素数が２０を越える場合は、原料の調達の困難さ及び純度の高いものの調達の困難さから好ましくない。炭化水素基としては、Ｒ¹，Ｒ²と同様のものが使用でき、炭素数１〜１０のアルキル基が好ましい。Ｓｉに直結する三級炭素を有する炭化水素基としては、例えば、ｔｅｒｔ．−ブチル基、ｔｅｒｔ．−アミル基、アダマンチル基等を挙げることができ、好ましくはｔｅｒｔ．−ブチル基である。前述の一般式（１）中、ｎは０〜２０の整数であり、好ましくは０〜１０の整数を表す。さらに好ましくは、０又は１である。
【００２４】
本発明における珪素含有アルケンは、具体的には、ビニルｔｅｒｔ．−ブチルジメチルシラン、アリルｔｅｒｔ．−ブチルジメチルシラン、ブテニルｔｅｒｔ．−ブチルジメチルシラン、ペンテニルｔｅｒｔ．−ブチルジメチルシラン、ヘキセニルｔｅｒｔ．−ブチルジメチルシラン、ヘプテニルｔｅｒｔ．−ブチルジメチルシラン、オクテニルｔｅｒｔ．−ブチルジメチルシラン、デセニルｔｅｒｔ．−ブチルジメチルシラン、ビニルジｔｅｒｔ．−ブチルメチルシラン、アリルジｔｅｒｔ．−ブチルメチルシラン、ブテニルジｔｅｒｔ．−ブチルメチルシラン、ペンテニルジｔｅｒｔ．−ブチルメチルシラン、ヘキセニルジｔｅｒｔ．−ブチルメチルシラン、ヘプテニルジｔｅｒｔ．−ブチルジメチルシラン、オクテニルジｔｅｒｔ．−ブチルメチルシラン、デセニルジｔｅｒｔ．−ブチルメチルシラン、ビニルｔｅｒｔ．−アミルジメチルシラン、アリルｔｅｒｔ．−アミルジメチルシラン、ブテニルｔｅｒｔ．−アミルジメチルシラン、ペンテニルｔｅｒｔ．−アミルジメチルシラン、ヘキセニルｔｅｒｔ．−アミルジメチルシラン、ヘプテニルｔｅｒｔ．−アミルジメチルシラン、オクテニルｔｅｒｔ．−アミルジメチルシラン、デセニルｔｅｒｔ．−アミルジメチルシラン、ビニルジｔｅｒｔ．−アミルメチルシラン、アリルジｔｅｒｔ．−アミルメチルシラン、ブテニルジｔｅｒｔ．−アミルメチルシラン、ペンテニルジｔｅｒｔ．−アミルメチルシラン、ヘキセニルジｔｅｒｔ．−アミルメチルシラン、ヘプテニルジｔｅｒｔ．−アミルジメチルシラン、オクテニルジｔｅｒｔ．−アミルメチルシラン、デセニルジｔｅｒｔ．−アミルメチルシラン、ビニルアダマンチルジメチルシラン、アリルアダマンチルジメチルシラン、ブテニルアダマンチルジメチルシラン、ペンテニルアダマンチルジメチルシラン、ヘキセニルアダマンチルジメチルシラン、ヘプテニルアダマンチルジメチルシラン、オクテニルアダマンチルジメチルシラン、デセニルアダマンチルジメチルシラン、ビニルジアダマンチルシラン、アリルジアダマンチルメチルシラン、ブテニルジアダマンチルメチルシラン、ペンテニルジアダマンチルメチルシラン、ヘキセニルジアダマンチルメチルシラン、ヘプテニルジアダマンチルジメチルシラン、オクテニルジアダマンチルメチルシラン、デセニルジアダマンチルメチルシランが挙げられる。
【００２５】
本発明において用いられる銅（Ｉ）化合物は、特に限定されるものではないが、塩化銅（Ｉ）、臭化銅（Ｉ）、沃化銅（Ｉ）等の銅（Ｉ）化合物を用いる方法、塩化銅（ＩＩ）、臭化銅（ＩＩ）、沃化銅（ＩＩ）等の銅（ＩＩ）化合物を還元剤等により還元した銅（Ｉ）化合物を用いる方法を採用することができる。
【００２６】
本発明の上記一般式（１）に示される安定化された珪素含有アルケン銅錯体の合成方法は、珪素含有アルケン共存下、下記一般式（２）の
【００２７】
【化４】

（式中、Ｒ¹，Ｒ²は、炭素数１〜２０の弗化炭化水素基、又は炭素数１〜２０の炭化水素基であり、Ｒ¹，Ｒ²の少なくとも一方は弗化炭化水素基である。Ｒ³は、水素原子、弗素原子、又は炭素数１〜２０の弗化炭化水素基を表わす。Ｍは、アルカリ金属を表わす。）で示されるβ−ジケトン金属塩に、銅（Ｉ）化合物を反応させることにより安定化された珪素含有アルケン銅錯体を得ることができる。
【００２８】
Ｒ¹，Ｒ²は、前述の一般式（１）におけるＲ¹，Ｒ²と同じであり、炭素数１〜２０の弗化炭化水素基、又は炭素数１〜２０の炭化水素基であり、Ｒ¹，Ｒ²の少なくとも一方は、弗化炭化水素基である。炭素数が２０を越える場合は、原料の調達の困難さ及び純度の高いものの調達の困難さから好ましくない。
【００２９】
Ｒ³は、前述の一般式（１）におけるＲ³と同じであり水素原子、弗素原子、又は炭素数１〜２０の弗化炭化水素基を表わす。炭素数が２０を越える場合は、原料の調達の困難さ及び純度の高いものの調達の困難さから好ましくない。
【００３０】
Ｍは、アルカリ金属であり、リチウム、ナトリウム、カリウム、ルビジウム、セシウムが挙げられる。
【００３１】
具体的には、例えば、弗化β−ジケトンに、珪素含有アルケン共存下、銅（Ｉ）化合物を反応させることにより合成することができる。珪素含有アルケンの非共存下にβ−ジケトン間の炭素上のプロトンをアルカリ金属で引き抜き、銅（Ｉ）化合物を反応させ、β−ジケトン銅錯体を合成した後、珪素含有アルケンを添加し配位させる方法を採用することも可能である。
【００３２】
安定化された珪素含有アルケン銅錯体を合成する際の溶媒は、当該技術分野で使用されるものであれば特に限定されるものではない。例えば、ｎ−ペンタン、ｉ−ペンタン、ｎ−ヘキサン、ｎ−ヘプタン、ｎ−デカン等の飽和炭化水素類、トルエン、キシレン、デセン−１等の不飽和炭化水素類、ジエチルエーテル、テトラヒドロフラン、テトラヒドロピラン等のエーテル類、ジクロロメタン、ジクロロエタン、クロロホルム、クロロベンゼン等のハロゲン化炭化水素類を挙げることができる。
【００３３】
安定化された珪素含有アルケン銅錯体を合成する際の反応温度は、特に限定されないが、生成する珪素含有アルケン銅錯体が分解しない様な温度範囲で行うことが好ましい。通常、工業的に使用されている温度である−７８〜２００℃の範囲、好ましくは、−５０〜１５０℃の範囲で行うことが好ましい。反応の圧力条件は、加圧下、常圧下、減圧下いずれであっても可能である。
【００３４】
合成した安定化された珪素含有アルケン銅錯体の精製方法は、特に限定されないが、減圧蒸留、及びシリカ，アルミナ，高分子ゲルを用いたカラム分離精製を使用することができる。この際の操作は、当該有機金属化合物合成分野における通常の方法が用いられる。すなわち、脱水及び脱酸素された窒素又はアルゴン雰囲気下で行い、使用する溶媒及び精製用のカラム充填剤等は、予め脱水操作を施しておくことが好ましい。この操作により、生成する安定化された珪素含有アルケン銅錯体の収量及び純度が向上する場合がある。
【００３５】
【実施例】
以下に実施例を示すが、本発明は、これらの実施例によって何ら限定されるものではない。
【００３６】
実施例１
窒素気流下２００ｍｌのシュレンク管に、１，１，１，５，５，５−ヘキサフルオロアセチルアセトン ２０．８１ｇ（０．１００ｍｏｌ）を脱水したテトラヒドロフラン １００ｍｌに希釈し、水素化カリウム ４．０１ｇ（０．１００ｍｏｌ）を添加した後、室温で攪拌してカリウム塩溶液とした。
【００３７】
得られたカリウム塩溶液を塩化銅（Ｉ） ９．９０ｇ（０．１００ｍｏｌ）とビニル−ｔｅｒｔ．−ブチルジメチルシラン １４．２１ｇ（０．１００ｍｏｌ）とテトラヒドロフラン １００ｍｌを混合したものに室温で滴下し、５０℃で４時間攪拌した。残渣をガラスフィルターで濾別した後、テトラヒドロフランを留去させ、減圧蒸留し、目的物である（１，１，１，５，５，５−ヘキサフルオロアセチルアセトナート）銅（Ｉ）ビニル−ｔｅｒｔ．−ブチルジメチルシラン３０．４３ｇ（０．０７２０ｍｏｌ）を得た。その結果、収率７２％であり、元素分析の結果は以下の通りであった。
Ｃ₁₃Ｈ₂₉Ｏ₂Ｆ₆ＳｉＣｕ ｗｔ％
測定値（Ｃ３６．７，Ｈ７．０，Ｆ２７．１，Ｃｕ１５．０，Ｓｉ６．６）
理論値（Ｃ３６．９，Ｈ６．９，Ｆ２７．０，Ｃｕ１５．０，Ｓｉ６．７）
実施例２
実施例１において、ビニル−ｔｅｒｔ．−ブチルジメチルシランに変えて、ビニル−ジｔｅｒｔ．−ブチルメチルシラン １８．４１ｇ（０．１００ｍｏｌ）としたこと以外は、実施例１と同様にして、（１，１，１，５，５，５−ヘキサフルオロアセチルアセトナート）銅（Ｉ）ビニル−ジｔｅｒｔ．−ブチルメチルシランの合成を行った。その結果は、収率６４％であり、元素分析の結果は、以下の通りであった。
Ｃ₁₆Ｈ₃₅Ｏ₂Ｆ₆ＳｉＣｕ ｗｔ％
測定値（Ｃ４１．１，Ｈ７．５，Ｆ２４．６，Ｃｕ１３．８，Ｓｉ６．１）
理論値（Ｃ４１．３，Ｈ７．５，Ｆ２４．５，Ｃｕ１３．７，Ｓｉ６．１）
実施例３
実施例１において、ビニル−ｔｅｒｔ．−ブチルジメチルシランに変えて、アリル−ｔｅｒｔ．−ブチルジメチルシラン １５．６１ｇ（０．１００ｍｏｌ）としたこと以外は、実施例１と同様にして、（１，１，１，５，５，５−ヘキサフルオロアセチルアセトナート）銅（Ｉ）アリル−ｔｅｒｔ．−ブチルジメチルシランの合成を行った。その結果は、収率７１％であり、元素分析の結果は、以下の通りであった。
Ｃ₁₄Ｈ₃₁Ｏ₂Ｆ₆ＳｉＣｕ ｗｔ％
測定値（Ｃ３８．６，Ｈ７．２，Ｆ２５．９，Ｃｕ１４．５，Ｓｉ６．３）
理論値（Ｃ３８．５，Ｈ７．１，Ｆ２６．１，Ｃｕ１４．６，Ｓｉ６．４）
【００３８】
【発明の効果】
以上、本発明によれば、熱安定性が高く、室温で蒸気圧を有する新規な銅錯体を得ることができ、殊に銅配線用ＭＯＣＶＤ材料として好適な銅錯体を得られる。
【００３９】
さらに、β−ジケトンを配位子として有する銅（Ｉ）錯体を合成するにあたり、極めて効率的で、経済的な合成処方を提供できる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a copper complex suitable for forming a copper thin film layer. More particularly, the present invention relates to a silicon-containing alkene copper complex suitable for use in forming a high-speed and high-integrated circuit wiring, that is, a copper wiring for a high-speed arithmetic circuit, by a chemical vapor deposition method and a method for producing the same.
[0002]
[Prior art]
In the manufacturing technology of the integrated circuit field of the electronics industry, there is an increasing demand for high integration and high speed. Currently, aluminum wiring is used in most integrated circuits, but with the demand for higher integration and higher speed, copper wiring technology with lower electrical resistance and migration resistance is being put into practical use.
[0003]
The copper wiring formation technique is a combination of a zero-valent copper (hereinafter referred to as copper (0)) sputtering method and a divalent copper (hereinafter referred to as copper (II)) solution plating method. And a chemical vapor deposition method (hereinafter referred to as MOCVD method) using an organometallic complex of monovalent copper (hereinafter referred to as copper (I)). However, it has been found that the former method combining the sputtering method and the plating method makes it difficult to fill a deep groove having a small diameter of about 0.15 μm or less. In order to solve this problem, the MOCVD method has been used, and it has become possible to cover grooves, holes, and steps having a high depth / caliber ratio (high aspect ratio) with a smooth and good film quality with small irregularities.
[0004]
Copper compounds include copper (II) bis (acetylsetnatate) and copper (II) bis (trimethylacetylacetonate), which are solid and have a low vapor pressure and are not suitable as a copper MOCVD material.
[0005]
In contrast, copper (II) bis (hexafluoroacetylacetonate) copper having a structure similar to these copper compounds and having fluorine as its ligand is a vapor pressure, although it is a solid. Has been used for a long time. This is due to the fact that the intermolecular interaction is reduced by fluorination. Copper (II) bis (hexafluoroacetylacetonate) copper and its hydrates are described by Van Herert et al. Electrochem. Soc. 112, 1123 (1965) have been reported for use as Cu-MOCVD materials. At this time, the copper compound is heated to 150 ° C., 90 ° C. hydrogen gas is used as a carrier gas, and copper (II) is deposited on the 250 ° C. substrate while being reduced to copper (0). At this time, the hexafluoroacetylacetonate anion, which is a ligand, is hydrogenated to become hexafluoroacetylacetone and discharged out of the system.
[0006]
A Cu-MOCVD material of a copper (II) compound using a Schiff base ligand, that is, a β-ketoimine ligand has also been proposed. For example, in US Pat. No. 3,594,216, bis (acetylacetone ethylenediimino) copper (II) and bis (acetylacetoneimino) copper (II) have been proposed and evaporated at 200 ° C. or higher and at 400 ° C. or higher. It is deposited on the substrate. Also, Mater. Res. Soc. Symp. Proc. 204, 415 (1990) proposes a copper (II) compound having a fluorinated Schiff base ligand, which is evaporated at a temperature of about 100 ° C. and evaporated on a substrate at a temperature of about 300 ° C. ing.
[0007]
In the above proposal, a deposition temperature of 200 ° C. or higher and a Cu-MOCVD material that can be deposited at a lower temperature have been desired.
[0008]
It is an organometallic compound of copper (I) that realizes the deposition temperature of 200 ° C. or less. Specifically, it is a cyclopentadienyl copper (I) trialkylphosphine complex, Chem. Mater. In 2,636 (1990), cyclopentadienyl copper (I) trimethylphosphine is deposited at a temperature of 130 ° C to 200 ° C. However, Cu-MOCVD using cyclopentadienyl copper (I) trialkylphosphine has problems such as phosphorus contamination on the substrate, selectivity to metals and insulators, and the like. Furthermore, cyclopentadienyl copper (I) trialkylphosphine itself has a problem of stability due to decomposition accompanied by precipitation of copper (0) even when used at a relatively low temperature around 70 ° C. for a long time. .
[0009]
Furthermore, it is solid like copper (II) described above, and has a problem that the evaporation rate and vapor deposition rate depend on the solid particle shape, particle size, and particle size distribution.
[0010]
The proposal of a liquid and relatively stable copper compound has been realized by a copper (I) complex coordinated with vinylsilane. Hexafluoroacetylacetonate copper (I) vinyltrimethylsilane proposed in Japanese Patent No. 2132893. Since it is liquid, the supply amount can be controlled by a liquid flow meter, the vapor pressure is relatively high, and it is easier to use as a MOCVD material than conventional solid compounds. However, because hexafluoroacetylacetonate copper (I) vinyltrimethylsilane is gradually decomposed by heating for a long time for vaporization, copper (0) is precipitated, or a vinylsilane compound is contained in the structure. In addition, when a vaporization operation is performed at a high temperature for a long time, oligomers and polymers thereof are generated, which may cause clogging in the apparatus.
[0011]
[Problems to be solved by the invention]
The present invention has been made in view of the above problems, and its object is to solve the problems of the prior art. That is, the object of the present invention is to form a copper thin film with a high vapor pressure and easy vaporization. It is an object to provide a copper complex for MOCVD that is easy to control and stable at high temperatures.
[0012]
[Means for Solving the Problems]
The present inventors have found that a copper compound having a acetylacetonate fluoride and a silicon-containing olefin having a specific structure as a ligand is thermally stable and has a high vapor pressure, that is, high-quality copper as an MOCVD material. The inventors have found a copper compound capable of forming a thin film at a controllable speed and have completed the present invention.
[0013]
That is, the present invention provides the following general formula (1)
[0014]
[Chemical 3]

(Wherein R ¹ and R ² are a fluorinated hydrocarbon group having 1 to 20 carbon atoms or a hydrocarbon group having 1 to 20 carbon atoms, and at least one of R ¹ and R ² is a fluorinated hydrocarbon group. R ³ represents a hydrogen atom, a fluorine atom, or a fluorinated hydrocarbon group having 1 to 20 carbon atoms, and R ⁴ , R ⁵ , and R ⁶ are hydrocarbon groups having 1 to 20 carbon atoms, One represents a hydrocarbon group having a tertiary hydrocarbon directly connected to Si, and n represents an integer of 0 to 20.) and a method for producing the same.
[0015]
Hereinafter, the present invention will be described in detail.
[0016]
The general formula (1) Oite, R ^1, R ² is a hydrocarbon group of fluorocarbon groups or 1 to 20 carbon atoms having 1 to 20 carbon atoms, at least one of fluoride of R ^1, R ² Hydrocarbon group. When the number of carbon atoms exceeds 20, it is not preferable because of difficulty in procuring raw materials and difficulty in procuring high purity materials.
[0017]
The fluorinated hydrocarbon group is not particularly limited as long as it is a hydrocarbon group having at least one fluorine atom, and examples thereof include a fluorinated saturated hydrocarbon group and a fluorinated unsaturated hydrocarbon group.
[0018]
Examples of the fluorinated saturated hydrocarbon group include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorocyclopropyl group, a perfluoromethylcyclopropyl group, a perfluorobutyl group, a perfluorocyclobutyl group, Perfluorocarbon residues such as perfluoropentyl group, perfluorocyclopentyl group, perfluoromethylcyclopentyl group, perfluorohexyl group, perfluorocyclohexyl group, perfluoro-1,2-dimethylcyclohexyl group, perfluoroheptyl group, fluoromethyl Group, difluoromethyl group, 1,1,1-trifluoroethyl group, 2-perfluoroalkylethyl group and other fluorohydrocarbon residues.
[0019]
Further, examples of the fluorinated unsaturated hydrocarbon group include perfluoroethenyl group, perfluoropropenyl group, perfluoro-1,3-butadienyl group, cyclobutenyl group, perfluoro-2-butynyl group, pentafluorophenyl group, A fluorotoluyl group, a bis (trifluoromethyl) phenyl group, a perfluoronaphthalenyl group, a perfluoroindenyl group, a perfluorofluorenyl group, and the like can be given.
[0020]
As a hydrocarbon group, it is a C1-C20 hydrocarbon group, Preferably the C1-C10 alkyl group, aryl group, arylalkyl group, and alkylaryl group can be mentioned. Specifically, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, tert. -Butyl group, n-pentyl group, tert. -Amyl group, n-hexyl group, cyclohexyl group, phenyl group, toluyl group and the like can be mentioned.
[0021]
When R ¹ and R ² are both fluorinated hydrocarbon groups, R ¹ and R ² may be the same or different.
[0022]
R ³ is the same fluorinated hydrocarbon group having 1 to 20 carbon atoms as R ¹ and R ² , preferably a fluorinated hydrocarbon group having 1 to 10 carbon atoms for increasing the vapor pressure of the copper complex, or a hydrogen atom Represents a fluorine atom. When the number of carbon atoms exceeds 20, it is not preferable because of difficulty in procuring raw materials and difficulty in procuring high purity materials.
[0023]
R ⁴ , R ⁵ and R ⁶ are each a hydrocarbon group having 1 to 20 carbon atoms, and at least one is a hydrocarbon group having a tertiary carbon directly bonded to Si. When the number of carbon atoms exceeds 20, it is not preferable because of difficulty in procuring raw materials and difficulty in procuring high purity materials. As the hydrocarbon group, those similar to R ¹ and R ² can be used, and an alkyl group having 1 to 10 carbon atoms is preferable. Examples of the hydrocarbon group having tertiary carbon directly connected to Si include tert. -Butyl group, tert. -An amyl group, an adamantyl group, etc. can be mentioned, Preferably tert. -A butyl group. In the above general formula (1), n is an integer of 0-20, preferably an integer of 0-10. More preferably, it is 0 or 1.
[0024]
Specifically, the silicon-containing alkene in the present invention is vinyl tert. -Butyldimethylsilane, allyl tert. -Butyldimethylsilane, butenyl tert. -Butyldimethylsilane, pentenyl tert. -Butyldimethylsilane, hexenyl tert. -Butyldimethylsilane, heptenyl tert. -Butyldimethylsilane, octenyl tert. -Butyldimethylsilane, decenyl tert. -Butyldimethylsilane, vinyl di tert. -Butylmethylsilane, allyl di tert. -Butylmethylsilane, butenyl di tert. -Butylmethylsilane, pentenyl di tert. -Butylmethylsilane, hexenyl di tert. -Butylmethylsilane, heptenyl di tert. -Butyldimethylsilane, octenyl di tert. -Butylmethylsilane, decenyl di tert. -Butylmethylsilane, vinyl tert. -Amyldimethylsilane, allyl tert. -Amyldimethylsilane, butenyl tert. -Amyldimethylsilane, pentenyl tert. -Amyldimethylsilane, hexenyl tert. -Amyldimethylsilane, heptenyl tert. -Amyldimethylsilane, octenyl tert. -Amyldimethylsilane, decenyl tert. -Amyldimethylsilane, vinyl di tert. -Amylmethylsilane, allyl di tert. -Amylmethylsilane, butenyl di tert. -Amylmethylsilane, pentenyl di tert. -Amylmethylsilane, hexenyl di tert. -Amylmethylsilane, heptenyl di tert. -Amyldimethylsilane, octenyl di tert. -Amylmethylsilane, decenyl di tert. -Amylmethylsilane, vinyladamantyldimethylsilane, allyladamantyldimethylsilane, butenyladamantyldimethylsilane, pentenyladamantyldimethylsilane, hexenyladamantyldimethylsilane, heptenyladamantyldimethylsilane, octenyladamantyldimethylsilane, decenyladamantyldimethylsilane, Vinyldiadamantylsilane, allyldiadamantylmethylsilane, butenyldiadamantylmethylsilane, pentenyldiadamantylmethylsilane, hexenyldiadamantylmethylsilane, heptenyldiadamantyldimethylsilane, octenyldiadamantylmethylsilane, decenyldiadamantylmethylsilane Is mentioned.
[0025]
The copper (I) compound used in the present invention is not particularly limited, but a method using a copper (I) compound such as copper (I) chloride, copper (I) bromide, copper (I) iodide or the like. A method using a copper (I) compound obtained by reducing a copper (II) compound such as copper chloride (II), copper bromide (II), copper iodide (II) or the like with a reducing agent can be employed.
[0026]
The method for synthesizing the stabilized silicon-containing alkene copper complex represented by the general formula (1) of the present invention is represented by the following general formula (2) in the presence of a silicon-containing alkene.
[Formula 4]

(Wherein R ¹ and R ² are a fluorinated hydrocarbon group having 1 to 20 carbon atoms or a hydrocarbon group having 1 to 20 carbon atoms, and at least one of R ¹ and R ² is a fluorinated hydrocarbon group. R ³ represents a hydrogen atom, a fluorine atom, or a fluorinated hydrocarbon group having 1 to 20 carbon atoms, M represents an alkali metal, and a β-diketone metal salt represented by copper (I ) A stabilized silicon-containing alkene copper complex can be obtained by reacting the compound.
[0028]
R ¹ and R ² are the same as R ¹ and R ² in the general formula (1), and are a fluorinated hydrocarbon group having 1 to 20 carbon atoms or a hydrocarbon group having 1 to 20 carbon atoms, At least one of R ¹ and R ² is a fluorinated hydrocarbon group. When the number of carbon atoms exceeds 20, it is not preferable because of difficulty in procuring raw materials and difficulty in procuring high purity materials.
[0029]
R ³ is the same as R ³ in the general formula (1) and represents a hydrogen atom, a fluorine atom, or a fluorinated hydrocarbon group having 1 to 20 carbon atoms. When the number of carbon atoms exceeds 20, it is not preferable because of difficulty in procuring raw materials and difficulty in procuring high purity materials.
[0030]
M is an alkali metal, and examples thereof include lithium, sodium, potassium, rubidium, and cesium.
[0031]
Specifically, it can be synthesized, for example, by reacting a fluorinated β-diketone with a copper (I) compound in the presence of a silicon-containing alkene. In the absence of a silicon-containing alkene, the proton on the carbon between the β-diketone is extracted with an alkali metal and reacted with a copper (I) compound to synthesize a β-diketone copper complex. It is also possible to adopt the method of making them.
[0032]
The solvent for synthesizing the stabilized silicon-containing alkene copper complex is not particularly limited as long as it is used in the technical field. For example, saturated hydrocarbons such as n-pentane, i-pentane, n-hexane, n-heptane and n-decane, unsaturated hydrocarbons such as toluene, xylene and decene-1, diethyl ether, tetrahydrofuran and tetrahydropyran And halogenated hydrocarbons such as dichloromethane, dichloroethane, chloroform, chlorobenzene and the like.
[0033]
Although the reaction temperature at the time of synthesizing the stabilized silicon-containing alkene copper complex is not particularly limited, it is preferably performed in a temperature range in which the generated silicon-containing alkene copper complex is not decomposed. Usually, it is carried out in the range of −78 to 200 ° C., preferably in the range of −50 to 150 ° C., which is a temperature used industrially. The pressure conditions for the reaction can be any of under pressure, normal pressure, and reduced pressure.
[0034]
The method for purifying the synthesized stabilized silicon-containing alkene copper complex is not particularly limited, and vacuum distillation and column separation purification using silica, alumina, and polymer gel can be used. For this operation, a normal method in the organometallic compound synthesis field is used. That is, the dehydration and deoxygenation is performed in a nitrogen or argon atmosphere, and the solvent to be used and the column filler for purification are preferably subjected to a dehydration operation in advance. This operation may improve the yield and purity of the resulting stabilized silicon-containing alkene copper complex.
[0035]
【Example】
Examples are shown below, but the present invention is not limited to these Examples.
[0036]
Example 1
In a 200 ml Schlenk tube under a nitrogen stream, dilute 20.81 g (0.100 mol) of 1,1,1,5,5,5-hexafluoroacetylacetone in 100 ml of dehydrated tetrahydrofuran, and 4.01 g (0.01 g) of potassium hydride. 100 mol), and stirred at room temperature to obtain a potassium salt solution.
[0037]
The obtained potassium salt solution was mixed with 9.90 g (0.100 mol) of copper (I) chloride and vinyl-tert. -To a mixture of 14.21 g (0.100 mol) of butyldimethylsilane and 100 ml of tetrahydrofuran was added dropwise at room temperature and stirred at 50 ° C for 4 hours. After the residue was filtered off with a glass filter, tetrahydrofuran was distilled off and distilled under reduced pressure to obtain (1,1,1,5,5,5-hexafluoroacetylacetonato) copper (I) vinyl-tert. . -30.43 g (0.0720 mol) of butyldimethylsilane was obtained. As a result, the yield was 72%, and the results of elemental analysis were as follows.
_{C 13 H 29 O 2 F 6} SiCu wt%
Measured value (C36.7, H7.0, F27.1, Cu15.0, Si6.6)
Theoretical values (C36.9, H6.9, F27.0, Cu15.0, Si6.7)
Example 2
In Example 1, vinyl-tert. -Instead of butyldimethylsilane, vinyl ditert. -(1,1,1,5,5,5-hexafluoroacetylacetonato) copper (I) vinyl, except that it was 18.41 g (0.100 mol) of butylmethylsilane. -Di tert. -Synthesis of butylmethylsilane was carried out. The result was a yield of 64%, and the results of elemental analysis were as follows.
C ₁₆ H ₃₅ O ₂ F ₆ SiCu wt%
Measured value (C41.1, H7.5, F24.6, Cu13.8, Si6.1)
Theoretical values (C41.3, H7.5, F24.5, Cu13.7, Si6.1)
Example 3
In Example 1, vinyl-tert. -Instead of butyldimethylsilane, allyl-tert. -(1,1,1,5,5,5-hexafluoroacetylacetonato) copper (I) allyl in the same manner as in Example 1 except that 15.61 g (0.100 mol) was used. -Tert. -Synthesis of butyldimethylsilane was carried out. As a result, the yield was 71%, and the results of elemental analysis were as follows.
_{C 14 H 31 O 2 F 6} SiCu wt%
Measured value (C38.6, H7.2, F25.9, Cu14.5, Si6.3)
Theoretical value (C38.5, H7.1, F26.1, Cu14.6, Si6.4)
[0038]
【The invention's effect】
As described above, according to the present invention, a novel copper complex having high thermal stability and having a vapor pressure at room temperature can be obtained, and in particular, a copper complex suitable as an MOCVD material for copper wiring can be obtained.
[0039]
Furthermore, when synthesizing a copper (I) complex having a β-diketone as a ligand, an extremely efficient and economical synthesis recipe can be provided.

Claims (4)

The following general formula (1)

(Wherein R ¹ and R ² are a fluorinated hydrocarbon group having 1 to 20 carbon atoms or a hydrocarbon group having 1 to 20 carbon atoms, and at least one of R ¹ and R ² is a fluorinated hydrocarbon group. R ³ represents a hydrogen atom, a fluorine atom, or a fluorinated hydrocarbon group having 1 to 20 carbon atoms, and R ⁴ , R ⁵ , and R ⁶ are hydrocarbon groups having 1 to 20 carbon atoms, One represents a hydrocarbon group having a tertiary hydrocarbon directly connected to Si, and n represents an integer of 0 to 20.). The silicon-containing alkene copper complex according to claim 1, wherein R ⁴ , R ⁵ , and R ⁶ are alkyl groups having 1 to 10 carbon atoms, and n is 0 or 1. At least one of R ⁴ , R ⁵ and R ⁶ is tert. The silicon-containing alkene copper complex according to claim 1 or 2, which is a -butyl group. In the presence of a silicon-containing alkene, the following general formula (2)

(Wherein R ¹ and R ² are a fluorinated hydrocarbon group having 1 to 20 carbon atoms or a hydrocarbon group having 1 to 20 carbon atoms, and at least one of R ¹ and R ² is a fluorinated hydrocarbon group. R ³ represents a hydrogen atom, a fluorine atom, or a fluorinated hydrocarbon group having 1 to 20 carbon atoms. M represents an alkali metal.) The method for producing a stabilized silicon-containing alkene copper complex according to any one of claims 1 to 3, wherein the compound is reacted.