JP4363052B2 - Copper complex having asymmetric β-diketone ligand and method for producing the same - Google Patents

Description

（式中、Ｒ¹は、水素原子又は炭素数１乃至２０の炭化水素基であり、Ｒ²は、炭素数１乃至２０の炭化水素基であり、Ｒ^fは、少なくとも一つの弗素原子を有する弗化炭化水素基である。Ｒ¹どうし，Ｒ²どうしは、同一でも異なってもよい。ｎは、０乃至２０の整数を表わす。）
で示される銅錯体及びその製造方法を提供することにあり、殊に上記一般式（１）で示される銅錯体は、Ｃｕ−ＭＯＣＶＤ材料として銅薄膜形成に有用である。
【００１３】
以下、本発明の詳細について説明する。
【００１４】
上記一般式（１）おいてＲ¹は、水素原子又は炭素数１乃至２０の炭化水素基であり、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乃至１０の炭化水素基である。Ｒ²は、炭素数１乃至２０、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乃至１０の炭化水素基である。Ｒ¹どうし、Ｒ²どうしは、同一であっても異なっても良い。
【００１５】
炭化水素基としては、特に限定されるものではないが、炭素数１〜２０、好ましくは炭素数１〜１０のアルキル基、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。
【００１６】
具体的には、例えば、メチル、エチル、ｎ−プロピル、ｉ−プロピル、ｎ−ブチル、ｉ−ブチル、ｓｅｃ−ブチル、ｔｅｒｔ．−ブチル、ｎ−ペンチル、ｔｅｒｔ．−アミル、ｎ−ヘキシル、シクロヘキシル、フェニル、トルイル基等をあげることができる。
【００１７】
Ｒ^fは、少なくとも一つの弗素原子を有する炭素数１〜２０の弗化炭化水素基である。弗化炭化水素基としては、少なくとも一つ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、炭素数１〜２０、好ましくは炭素数１〜１０の弗化飽和炭化水素基や弗化不飽和炭化水素基等をあげることができる。
【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は、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】
ｎは、０乃至２０の整数、好ましくは０乃至１０の整数、特に好ましくは０乃至２の整数を表す。
【００２１】
続いて、上記一般式（１）の非対称βジケトン配位銅錯体の製造の際に用いることができる原料について説明する。
【００２２】
銅（Ｉ）原料としては、酸化第一銅を用いることができる。
【００２３】
シリル基置換アルケンとしては、下記一般式（２）のシリル基置換アルケンを用いることができる。
【００２４】
【化５】

（式中、Ｒ²およびｎは、上記に同じ。）
βジケトン成分としては、下記一般式（３）のβジケトンを用いることができる。
【００２５】
【化６】

（式中、Ｒ¹、Ｒ^fは、上記に同じ。）
一般式（１）の非対称βジケトン配位銅錯体の製造方法については、一般式（２）のシリル基置換アルケンの共存下、一般式（３）のβジケトンに酸化第一銅を反応させることによって製造することができる。
【００２６】
この際の量論比については、特に限定されないが、β−ジケトン１ｍｏｌに対し、酸化第一銅が０．０１ｍｏｌ乃至１００ｍｏｌ、好ましくは、０．５ｍｏｌ乃至５０ｍｏｌ、特に好ましくは、０．１ｍｏｌ乃至１０ｍｏｌの範囲であり、シリル基置換アルケンが０．０１ｍｏｌ乃至５００ｍｏｌ、好ましくは、０．５ｍｏｌ乃至２５０ｍｏｌ、特に好ましくは、０．１ｍｏｌ乃至５０ｍｏｌの範囲で添加することができる。この範囲を外れた場合、目的物である非対称βジケトン配位銅錯体の収量が低くなったり、精製が困難となる場合がある。
【００２７】
一般式（２）のシリル基置換アルケンの共存下、一般式（３）のβジケトンに酸化第一銅を反応させる場合、副生する水をモレキュラーシーブ、硫酸マグネシウム、硫酸ナトリウム、炭酸ナトリウム等の脱水剤を共存させて除去することが好ましい。脱水剤を共存させることにより、目的物の非対称βジケトン配位銅錯体の収率が向上する場合がある。
【００２８】
非対称βジケトン配位銅錯体を製造する際、溶媒非存在下、又は溶媒存在下で反応を行うことができる。溶媒の種類は、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。
【００２９】
しかしながら、溶媒希釈しない製造法を用いることにより、非対称βジケトン配位銅錯体の顕著な収率向上及び反応器当りの収量向上が観られる場合がある。
【００３０】
銅錯体を製造する際の反応温度については、特に限定されないが、生成する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。
【００３１】
製造された非対称βジケトン配位銅錯体の精製法について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での方法に従えばよい。すなわち、例えば、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、生成する銅錯体の収量及び純度が向上する場合がある。
【００３２】
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。
【００３３】
【実施例】
実施例１
窒素気流下、攪拌装置を有する５００ｍｌのシュレンク管に１，１，１−トリフルオロ−５，５−ジメチル−２，４−ヘキサンジオン２８．２ｇ（１４４ｍｍｏｌ）、酸化第一銅２４．７ｇ（１７３ｍｍｏｌ）、ビニルトリメトキシシラン６４．０ｇ（４３２ｍｍｏｌ）、乾燥ｎ−ペンタン３００ｍｌ、モレキュラーシーブ５０ｍｌを仕込み、室温で２４時間攪拌反応させた。モレキュラーシーブ及び未反応の酸化第一銅をガラスフィルターで除去し、濾液から、未反応の１，１，１−トリフルオロ−５，５−ジメチル−２，４−ヘキサンジオン及びビニルトリメトキシシランを減圧条件下留去し、更に減圧蒸留により、目的物である１，１，１−トリフルオロ−５，５−ジメチル−２，４−ヘキサンジオナト）銅（Ｉ）ビニルトリメトキシシランの濃青色液体３３．９ｇ（８３．３ｍｏｌ）を蒸留単離した。収率は、５７．９％（ヘキサンジオン基準）に相当した。
【００３４】
目的物の元素分析及び¹Ｈ−ＮＭＲの結果は以下の通りであった。
Ｃ₁₃Ｈ₂₂Ｏ₅Ｆ₃ＳｉＣｕ （ｗｔ％）
測定値（Ｃ：３８．１，Ｈ：５．６，Ｆ：１４．１，Ｃｕ：１５．４，Ｓｉ：６．９）
計算値（Ｃ：３８．４，Ｈ：５．５，Ｆ：１４．０，Ｃｕ：１５．６，Ｓｉ：６．９）
¹Ｈ−ＮＭＲ（ｉｎ Ｃ₆Ｄ₆） δ１．０３ｐｐｍ（９Ｈ，ｓ，ＳｉОＣＨ ₃ ）、δ３．４７ｐｐｍ（９Ｈ，ｓ，（Ｈ ₃Ｃ）₃Ｃ（Ｃ＝Ｏ））、δ４．２０〜４．８３ｐｐｍ（３Ｈ，ｍ，ＣＨ ₂ ＣＨ−）、δ６．１２ｐｐｍ（１Ｈ，ｓ，（Ｃ＝Ｏ）ＣＨ（Ｃ＝Ｏ））
実施例２
実施例１において溶媒であるｎ−ペンタンを添加せず、ビニルトリメトキシシランの量を１０６．６ｇ（７１９ｍｍｏｌ）としたこと以外は、実施例１と同様に目的物である１，１，１−トリフルオロ−５，５−ジメチル−２，４−ヘキサンジオナト）銅（Ｉ）ビニルトリメトキシシランを合成し、減圧蒸留単離した。結果は、目的物の濃青色液体を収率８３．３％で得た。無溶媒条件での合成で明確な収率向上が認められた。
【００３５】
実施例３
実施例１において、１，１，１−トリフルオロ−５，５−ジメチル−２，４−ヘキサンジオンに変えて、１，１，１−トリフルオロアセチルアセトン用いたこと以外は、実施例１と同様にして目的物である（１，１，１−トリフルオロアセチルアセトナト）銅（Ｉ）ビニルトリメトキシシランの緑色液体を得た。収率は、５４．９％であった。本目的物の元素分析及び¹Ｈ−ＮＭＲの結果は以下の通りであった。
【００３６】
Ｃ₁₀Ｈ₁₆Ｏ₅Ｆ₃ＳｉＣｕ （ｗｔ％）
測定値（Ｃ：３２．８，Ｈ：４．４，Ｆ：１５．５，Ｃｕ：１６．８，Ｓｉ：７．６）
計算値（Ｃ：３２．９，Ｈ：４．４，Ｆ：１５．６，Ｃｕ：１７．４，Ｓｉ：７．７）
¹Ｈ−ＮＭＲ（ｉｎ Ｃ₆Ｄ₆） δ１．６９３ｐｐｍ（３Ｈ，ｓ，ＣＨ ₃ （Ｃ＝Ｏ））、δ３．４７９ｐｐｍ（３Ｈ，ｓ，Ｓｉ（ОＣＨ₃）₃）、δ３．９５〜４．６３ｐｐｍ（３Ｈ，ｍ，ＣＨ₂＝ＣＨ−）、δ５．７０８ｐｐｍ（１Ｈ，ｓ，（Ｃ＝Ｏ）ＣＨ（Ｃ＝Ｏ））
比較例１
実施例１において、１，１，１−トリフルオロ−５，５−ジメチル−２，４−ヘキサンジオンに変えて、１，１，１−トリフルオロアセチルアセトン用い、ビニルトリメトキシシランに変えて、ビニルトリメチルシランを用いたこと以外は、実施例１と同様にして、目的物である（１，１，１−トリフルオロアセチルアセトナト）銅（Ｉ）ビニルトリメチルシランの濃青色液体を得た。収率は、５７．１％であった。本濃青色液体の¹Ｈ−ＮＭＲは、以下の通りであった。
【００３７】
¹Ｈ−ＮＭＲ（ｉｎ Ｃ₆Ｄ₆） δ０．０６８ｐｐｍ（９Ｈ，ｓ，ＳｉＣＨ₃）、δ１．７４ｐｐｍ（３Ｈ，ｓ，ＣＨ₃（Ｃ＝Ｏ））、δ４．１２ｐｐｍ（３Ｈ，ｂｒｏａｄ，ＣＨ₂＝ＣＨ−）、δ５．７３ｐｐｍ（１Ｈ，ｓ，（Ｃ＝Ｏ）ＣＨ（Ｃ＝Ｏ））
しかしながら、本１，１，１−トリフルオロアセチルアセトナト）銅（Ｉ）ビニルトリメチルシランの濃青色液体を窒素雰囲気下、室温にて３時間放置したところ、緑色固体及び黄金色の金属銅が析出し、目的物の液体がすべて固化した。すなわち、室温で本銅錯体が不安定で分解し易く、ＭＯＣＶＤ材料としては不適であることが認められた。
【００３８】
比較例２
［非対称βジケトンアルカリ金属塩の製造］
窒素気流下、攪拌装置を有する５００ｍｌのシュレンク管に、１，１，１−トリフルオロ−５，５−ジメチル−２，４−ヘキサンジオン２８．１ｇ（１４３ｍｍｏｌ）を、脱水したテトラヒドロフラン４００ｍｌに希釈し、８５％純度の水酸化カリウム９．４６ｇ（１４３ｍｍｏｌ）及びモレキュラーシーブ２００ｍｌを添加し、室温で４時間攪拌し１，１，１−トリフルオロ−５，５−ジメチル−２，４−ヘキサンジオンのカリウム塩溶液を得た。反応後、モレキュラーシーブをガラスフィルターで除去し、得られた濾液からテトラヒドロフランを減圧留去し、ｎ−ペンタンでスラリー化し、ガラスフィルターで目的物である１，１，１−トリフルオロ−５，５−ジメチル−２，４−ヘキサンジオンのカリウム塩２０．５ｇ（８７．４ｍｍｏｌ）を得た。収率は、６１．０％であった。
［非対称βジケトン配位銅（Ｉ）錯体の製造］
窒素気流下、攪拌装置を有する２００ｍｌのシュレンク管に１，１，１−トリフルオロ−５，５−ジメチル−２，４−ヘキサンジオンのカリウム塩７．０３ｇ（３０．０ｍｍｏｌ）、塩化第一銅３．５６ｇ（３６．０ｍｍｏｌ）、ビニルトリメトキシシラン２２．２ｇ（１５０ｍｍｏｌ）を仕込み、これに乾燥ｎ−ペンタン１５０ｍｌを加え、反応を開始した。室温で２７時間反応させた後、未反応物及び副生物である塩化カリウムをガラスフィルターで除去し、得られた濾液からｎ−ペンタンを留去したが、青緑色の固体が得られたのみであった。元素分析を行ったところＣｕ含有量が５．２ｗｔ％であった。計算値１５．６ｗｔ％とはかけ離れており、目的の錯体が合成されていないことが判明した。
【００３９】
【発明の効果】
本発明によれば、以下の顕著な効果が奏される。
【００４０】
本発明の第一の効果としては、従来の弗素含有βジケトン銅（Ｉ）ビニルシラン錯体よりも弗素含有量が低く、安定であり、蒸気圧が高い新規な銅錯体を提供することが可能となった。殊に本錯体は、銅配線用ＭＯＣＶＤ材料として好適である。
【００４１】
第二の効果としては、非対称β−ジケトンを配位子として有する銅（Ｉ）錯体を製造するにあたり、極めて効率的で、経済的な合成処方を提供することが可能となった。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a copper complex suitable for forming a copper thin film layer and a method for producing the same. In particular, the present invention relates to a copper complex suitable for use in forming a high-speed 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 manufacturing 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]
Regarding the copper wiring formation technology, a method combining a zero-valent Cu sputtering method and a solution plating method of divalent Cu, and a chemical vapor deposition method (hereinafter referred to as MOCVD method) mainly using an organometallic complex of monovalent Cu, There is. However, in the former method in which the sputtering method and the plating method are combined, it is difficult to fill a deep groove having a small diameter of about 0.07 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]
Various types of MOCVD copper compounds are already known. For example, Patent Document 1 proposes to use 1,1,1,5,5,5-hexafluoroacetylacetonato copper (I) vinyltrimethylsilane. Since the present copper compound is in a liquid state, the supply amount can be controlled by a liquid flow meter, the vapor pressure is relatively high, and it is easier to use as an MOCVD material than a conventional solid compound.
[0005]
However, the hexafluoroacetylacetonate copper (I) vinyltrimethylsilane is gradually decomposed by heating for a long time for vaporization, and Cu (O) is precipitated, and oligomers and polymers of trimethylvinylsilane are produced. There was a case that became the cause of blockage in the inside. Furthermore, since hexafluoroacetylacetonate copper (I) vinyltrimethylsilane has a high fluorine content, when a copper wiring for LSI is formed by MOCVD using this, fluorine remains in the copper wiring composition, TaN, There is a problem that the adhesion to a barrier metal such as TiN is extremely inferior to that obtained by sputtering. Therefore, a copper compound having a low fluorine content is demanded.
[0006]
In order to solve this problem, the present inventors have already proposed copper compounds disclosed in Patent Document 2 and Patent Document 3. However, the vapor pressures of the copper compounds proposed in these patent documents are insufficient for realizing a high film formation rate. There is a need for stable copper compounds with higher vapor pressures.
[0007]
That is, there is always a demand for a high-performance copper compound from the market, in particular, low fluorine content, high vapor pressure characteristics, stable within the vaporization temperature range, at a relatively low temperature of about 200 ° C. Copper complexes that can be decomposed and deposited are highly desired.
[0008]
[Patent Document 1]
Patent No. 2132693 [Patent Document 2]
JP 2002-193974 A [Patent Document 3]
Japanese Patent Laid-Open No. 2002-199398
[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 present invention has a high vapor pressure, is stable and easy to vaporize, and is a copper thin film. It is an object of the present invention to provide a copper complex for MOCVD having a low fluorine content capable of controlling the formation rate of the.
[0010]
[Means for Solving the Problems]
The present inventors have found that a copper compound having a combination of an asymmetric β-diketone ligand and a silyl group-substituted olefin ligand having a specific structure is thermally stable, has a high vapor pressure, and is a high-quality copper thin film as an MOCVD material. The present inventors have found a copper compound that can be formed at a controllable speed, and have completed the present invention.
[0011]
That is, the present invention provides the following general formula (1)
[0012]
[Formula 4]

Wherein R ¹ is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, R ² is a hydrocarbon group having 1 to 20 carbon atoms, and R ^f has at least one fluorine atom. (It is a fluorinated hydrocarbon group. R ¹ and R ² may be the same or different. N represents an integer of 0 to 20.)
In particular, the copper complex represented by the general formula (1) is useful for forming a copper thin film as a Cu-MOCVD material.
[0013]
Details of the present invention will be described below.
[0014]
In the general formula (1), R ¹ is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, preferably a hydrocarbon group having 1 to 10 carbon atoms in order to increase the vapor pressure of the copper complex. is there. R ² is a hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms for increasing the vapor pressure of the copper complex. R ¹ and R ² may be the same or different.
[0015]
Although it does not specifically limit as a hydrocarbon group, C1-C20, Preferably a C1-C10 alkyl group, an aryl group, an arylalkyl group, and an alkylaryl group can be mentioned.
[0016]
Specifically, for example, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, tert. -Butyl, n-pentyl, tert. -Amyl, n-hexyl, cyclohexyl, phenyl, toluyl group and the like can be mentioned.
[0017]
R ^f is a fluorinated hydrocarbon group having 1 to 20 carbon atoms having at least one fluorine atom. The fluorinated hydrocarbon group is not particularly limited as long as it is a hydrocarbon group having at least one fluorine atom, and is a fluorinated saturated hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms. Examples thereof include 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 fluorohydrocarbon residue and the like.
[0019]
Furthermore, examples of the fluorinated unsaturated hydrocarbon group include a perfluoroethenyl group, a perfluoropropenyl group, a perfluoro-1,3-butadienyl group, a cyclobutenyl group, a perfluoro-2-butynyl group, a pentafluorophenyl group, A perfluorotoluyl group, a bis (trifluoromethyl) phenyl group, a perfluoronaphthalenyl group, a perfluoroindenyl group, a perfluorofluorenyl group, and the like can be given.
[0020]
n represents an integer of 0 to 20, preferably an integer of 0 to 10, particularly preferably an integer of 0 to 2.
[0021]
Then, the raw material which can be used in the case of manufacture of the asymmetric beta diketone coordination copper complex of the said General formula (1) is demonstrated.
[0022]
As the copper (I) raw material, cuprous oxide can be used.
[0023]
As the silyl group-substituted alkene, a silyl group-substituted alkene represented by the following general formula (2) can be used.
[0024]
[Chemical formula 5]

(In the formula, R ² and n are the same as above.)
As the β-diketone component, a β-diketone represented by the following general formula (3) can be used.
[0025]
[Chemical 6]

(In the formula, R ¹ and R ^f are the same as above.)
About the manufacturing method of the asymmetrical β-diketone coordination copper complex of the general formula (1), reacting the cuprous oxide with the β-diketone of the general formula (3) in the presence of the silyl group-substituted alkene of the general formula (2). Can be manufactured by.
[0026]
The stoichiometric ratio at this time is not particularly limited, but cuprous oxide is 0.01 mol to 100 mol, preferably 0.5 mol to 50 mol, particularly preferably 0.1 mol to 10 mol, relative to 1 mol of β-diketone. The silyl group-substituted alkene can be added in an amount of 0.01 mol to 500 mol, preferably 0.5 mol to 250 mol, particularly preferably 0.1 mol to 50 mol. If it is out of this range, the yield of the target asymmetric β-diketone coordination copper complex may be low, or purification may be difficult.
[0027]
When reacting cuprous oxide with β-diketone of general formula (3) in the coexistence of silyl group-substituted alkene of general formula (2), water produced as a by-product is used as molecular sieve, magnesium sulfate, sodium sulfate, sodium carbonate, etc. It is preferable to remove in the presence of a dehydrating agent. In the presence of a dehydrating agent, the yield of the target asymmetric β-diketone coordination copper complex may be improved.
[0028]
When producing an asymmetric β-diketone coordination copper complex, the reaction can be carried out in the absence of a solvent or in the presence of a solvent. The kind of solvent will not be specifically limited if it is used in the said 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.
[0029]
However, by using a production method that does not dilute the solvent, a significant yield improvement of the asymmetric β-diketone coordination copper complex and a yield improvement per reactor may be observed.
[0030]
The reaction temperature at the time of producing the copper complex is not particularly limited, but it is preferably performed in a temperature range in which the produced 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.
[0031]
Although the purification method of the produced asymmetric β-diketone coordination copper complex is not particularly limited, vacuum distillation and column separation purification using silica, alumina, and polymer gel can be used. The operation at this time may follow the method in the organometallic compound synthesis field. That is, for example, 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 dehydration operations in advance. By this operation, the yield and purity of the produced copper complex may be improved.
[0032]
Examples are shown below, but the present invention is not limited to these Examples.
[0033]
【Example】
Example 1
In a 500 ml Schlenk tube equipped with a stirrer under a nitrogen stream, 28.2 g (144 mmol) of 1,1,1-trifluoro-5,5-dimethyl-2,4-hexanedione and 24.7 g (173 mmol) of cuprous oxide were added. ), Vinyltrimethoxysilane (64.0 g, 432 mmol), dry n-pentane (300 ml) and molecular sieve (50 ml) were charged, and the mixture was stirred at room temperature for 24 hours. The molecular sieve and unreacted cuprous oxide are removed with a glass filter, and unreacted 1,1,1-trifluoro-5,5-dimethyl-2,4-hexanedione and vinyltrimethoxysilane are removed from the filtrate. Distilled off under reduced pressure, and further distilled under reduced pressure to obtain 1,1,1-trifluoro-5,5-dimethyl-2,4-hexanedionato) copper (I) vinyltrimethoxysilane as a deep blue color. 33.9 g (83.3 mol) of liquid was isolated by distillation. The yield corresponded to 57.9% (based on hexanedione).
[0034]
The results of elemental analysis and ¹ H-NMR of the target product were as follows.
_{C 13 H 22 O 5 F 3} SiCu (wt%)
Measured value (C: 38.1, H: 5.6, F: 14.1, Cu: 15.4, Si: 6.9)
Calculated value (C: 38.4, H: 5.5, F: 14.0, Cu: 15.6, Si: 6.9)
_{^{1 H-NMR (in C 6}} D 6) δ1.03ppm (9H, s, SiОC H 3), δ3.47ppm (9H, s, (H 3 C) 3 C (C = O)), δ4.20~ 4.83 ppm (3H, m, C H ₂ C H −), δ 6.12 ppm (1 H, s, (C═O) C H (C═O))
Example 2
The target product 1,1,1- is the same as in Example 1 except that n-pentane as a solvent in Example 1 is not added and the amount of vinyltrimethoxysilane is 106.6 g (719 mmol). (Trifluoro-5,5-dimethyl-2,4-hexanedionato) copper (I) vinyltrimethoxysilane was synthesized and isolated by distillation under reduced pressure. As a result, the target dark blue liquid was obtained in a yield of 83.3%. A clear improvement in yield was observed in the synthesis under solvent-free conditions.
[0035]
Example 3
Example 1 is the same as Example 1 except that 1,1,1-trifluoro-5,5-dimethyl-2,4-hexanedione is used instead of 1,1,1-trifluoroacetylacetone. As a result, a green liquid of (1,1,1-trifluoroacetylacetonato) copper (I) vinyltrimethoxysilane which was the target product was obtained. The yield was 54.9%. The results of elemental analysis and ¹ H-NMR of the target product were as follows.
[0036]
_{C 10 H 16 O 5 F 3} SiCu (wt%)
Measured value (C: 32.8, H: 4.4, F: 15.5, Cu: 16.8, Si: 7.6)
Calculated value (C: 32.9, H: 4.4, F: 15.6, Cu: 17.4, Si: 7.7)
¹ H-NMR (in C ₆ D ₆ ) δ 1.593 ppm (3H, s, C H ₃ (C═O)), δ 3.479 ppm (3H, s, Si (ОCH ₃ ) ₃ ), δ 3.95-4 .63 ppm (3H, m, CH ₂ ═CH—), δ 5.708 ppm (1H, s, (C═O) CH (C═O))
Comparative Example 1
In Example 1, 1,1,1-trifluoro-5,5-dimethyl-2,4-hexanedione was used instead of 1,1,1-trifluoroacetylacetone, and vinyltrimethoxysilane was used instead of vinyl. Except for using trimethylsilane, a dark blue liquid of (1,1,1-trifluoroacetylacetonato) copper (I) vinyltrimethylsilane which was the target product was obtained in the same manner as in Example 1. The yield was 57.1%. ¹ H-NMR of this dark blue liquid was as follows.
[0037]
¹ H-NMR (in C ₆ D ₆ ) δ 0.068 ppm (9H, s, SiCH ₃ ), δ 1.74 ppm (3H, s, CH ₃ (C═O)), δ 4.12 ppm (3H, broadcast, CH ₂ = CH-), δ 5.73 ppm (1H, s, (C = O) CH (C = O))
However, when this 1,1,1-trifluoroacetylacetonato) copper (I) vinyltrimethylsilane dark blue liquid was allowed to stand at room temperature for 3 hours in a nitrogen atmosphere, a green solid and golden metallic copper precipitated. As a result, all of the target liquid solidified. That is, it was recognized that the copper complex is unstable and easily decomposed at room temperature and is not suitable as an MOCVD material.
[0038]
Comparative Example 2
[Production of asymmetric β-diketone alkali metal salt]
Under a nitrogen stream, 28.1 g (143 mmol) of 1,1,1-trifluoro-5,5-dimethyl-2,4-hexanedione was diluted in 400 ml of dehydrated tetrahydrofuran in a 500 ml Schlenk tube equipped with a stirrer. , 85% purity potassium hydroxide 9.46 g (143 mmol) and molecular sieve 200 ml were added, stirred at room temperature for 4 hours, and 1,1,1-trifluoro-5,5-dimethyl-2,4-hexanedione A potassium salt solution was obtained. After the reaction, the molecular sieve was removed with a glass filter. Tetrahydrofuran was distilled off from the resulting filtrate under reduced pressure, slurried with n-pentane, and the target 1,1,1-trifluoro-5,5 was obtained with a glass filter. -20.5 g (87.4 mmol) of potassium salt of dimethyl-2,4-hexanedione was obtained. The yield was 61.0%.
[Production of Asymmetric β-Diketone Coordinated Copper (I) Complex]
Under a nitrogen stream, 7.03 g (30.0 mmol) of potassium salt of 1,1,1-trifluoro-5,5-dimethyl-2,4-hexanedione and cuprous chloride in a 200 ml Schlenk tube equipped with a stirrer 3.56 g (36.0 mmol) and vinyltrimethoxysilane 22.2 g (150 mmol) were charged, and 150 ml of dry n-pentane was added thereto to initiate the reaction. After reacting at room temperature for 27 hours, unreacted substances and by-product potassium chloride were removed with a glass filter, and n-pentane was distilled off from the obtained filtrate, but only a blue-green solid was obtained. there were. Upon elemental analysis, the Cu content was 5.2 wt%. It was far from the calculated value of 15.6 wt%, and it was found that the target complex was not synthesized.
[0039]
【The invention's effect】
According to the present invention, the following remarkable effects are exhibited.
[0040]
As the first effect of the present invention, it is possible to provide a novel copper complex having a lower fluorine content, more stable, and higher vapor pressure than conventional fluorine-containing β-diketone copper (I) vinylsilane complexes. It was. In particular, this complex is suitable as a MOCVD material for copper wiring.
[0041]
As a second effect, it has become possible to provide an extremely efficient and economical synthetic recipe for producing a copper (I) complex having an asymmetric β-diketone as a ligand.

Claims (3)

The following general formula (1)

(In the formula, ^{R 1} is a hydrogen atom or a methyl group, ^{R 2} is a methyl group, ^{R f} is what .R ¹ is a trifluoromethyl group represents 0 good .n is be the same or different. ) Copper complex. In the presence of a silyl group-substituted alkene of the following general formula (2),

(In the formula, R ² is a methyl group, and n represents 0. )
Β diketone of the following general formula (3) and

(In the formula, R ¹ is a hydrogen atom or a methyl group, and R ^f is a trifluoromethyl group . R ¹ may be the same or different. )
General formula (1) characterized by reacting cuprous oxide

(Wherein R ¹ , R ² , R ^f and n are the same as above) . Without adding a solvent, a silyl group substituted alkene, beta diketo emission and a manufacturing method of the copper complex of claim 2, wherein the reacting cuprous oxide.