JP2001114789A - Organic copper compound for metal organic chemical vapor deposition and solution raw material containing the same and used for forming thin copper film and thin copper film formed from the same - Google Patents
Organic copper compound for metal organic chemical vapor deposition and solution raw material containing the same and used for forming thin copper film and thin copper film formed from the sameInfo
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- JP2001114789A JP2001114789A JP28806699A JP28806699A JP2001114789A JP 2001114789 A JP2001114789 A JP 2001114789A JP 28806699 A JP28806699 A JP 28806699A JP 28806699 A JP28806699 A JP 28806699A JP 2001114789 A JP2001114789 A JP 2001114789A
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- copper
- hexafluoroacetylacetone
- thin film
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、半導体装置の配線
に用いられる銅（Ｃｕ）薄膜を有機金属化学蒸着（Meta
l Organic Chemical Vapor Deposition、以下、ＭＯＣ
ＶＤという。）法により作製するための有機金属化学蒸
着用有機銅化合物及びこれを含む銅薄膜形成用溶液原料
並びにこれから作られた銅薄膜に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of depositing a copper (Cu) thin film used for wiring of a semiconductor device by metal organic chemical vapor deposition (Meta
l Organic Chemical Vapor Deposition, MOC
It is called VD. The present invention relates to an organocopper compound for metalorganic chemical vapor deposition, a solution raw material for forming a copper thin film containing the same, and a copper thin film produced therefrom.
【０００２】[0002]
【従来の技術】ＭＯＣＶＤ法に用いられる有機銅化合物
として、厳格な化学的、構造的かつ電気的広範な必要条
件の組合せを充足させる選択蒸着能力のある室温で液体
の錯体銅+1ｔｍｖｓ・ｈｆａｃ（ｔｍｖｓはトリメチル
ビニルシランの略語で、ｈｆａｃはヘキサフルオロアセ
チルアセトン陰イオンの略語である）が良く知られてい
る（特開平５−２０２４７６）。しかしこの化合物は極
めて安定性に欠け、室温で容易に分解し、金属銅の析出
と副生成物の銅+2（ｈｆａｃ）2に変化し劣化が著し
い。そのため、この有機銅化合物は成膜時に安定して供
給することが難しく、成膜の再現性に劣る。2. Description of the Prior Art As an organic copper compound used in the MOCVD method, a complex liquid copper at room temperature having a selective vapor deposition ability satisfying a strict combination of strict chemical, structural and electrical requirements + 1 room temperature tmvs · hfac (Tmvs is an abbreviation for trimethylvinylsilane and hfac is an abbreviation for hexafluoroacetylacetone anion) is well known (JP-A-5-202476). However, this compound has extremely low stability, easily decomposes at room temperature, changes into copper +2 (hfac) 2 as a by-product of metal copper, and is remarkably deteriorated. Therefore, it is difficult to stably supply this organic copper compound during film formation, and the reproducibility of film formation is poor.
【０００３】この点を解決するために、上記有機銅化合
物よりも安定した気化速度を得られるとともに優れた揮
発性と熱安定性を示す室温で液体の銅+1ａｔｍｓ・ｈｆ
ａｃ（ａｔｍｓはアリルトリメチルシランの略語であ
る）が開示されている（特開平７−２５２２６６、特開
平１０−１３５１５４）。一方、銅+1ｈｆａｃと(メト
キシ)(メチル)シリロレフィンリガンドを含み、気化温
度まで加熱されると、(メトキシ)(メチル)シリロレフィ
ンリガンド内の酸素の電子供与能力が銅と(メトキシ)
(メチル)シリロレフィンリガンドとの間に安定な結合を
提供する銅プリカーサ化合物が提案されている（特開平
１０−１９５６５４）。この銅プリカーサ化合物では、
メトキシ基の酸素原子が主に銅プリカーサ化合物の揮発
性を抑制し、銅プリカーサ化合物の温度安定性及び寿命
を向上させることができる。In order to solve this problem, a liquid copper at room temperature, which can obtain a more stable vaporization rate than the above-mentioned organocopper compound and exhibits excellent volatility and thermal stability, and at least 1 atms · hf
ac (atms is an abbreviation for allyltrimethylsilane) is disclosed (JP-A-7-252266, JP-A-10-135154). On the other hand, when copper +1 hfac and (methoxy) (methyl) silylolefin ligand are contained and heated to the vaporization temperature, the electron donating ability of oxygen in the (methoxy) (methyl) silylolefin ligand becomes copper and (methoxy). )
A copper precursor compound that provides a stable bond with a (methyl) silylolefin ligand has been proposed (JP-A-10-195654). In this copper precursor compound,
The oxygen atom of the methoxy group mainly suppresses the volatility of the copper precursor compound, and can improve the temperature stability and life of the copper precursor compound.
【０００４】[0004]
【発明が解決しようとする課題】しかし、銅+1ｔｍｖｓ
・ｈｆａｃは勿論のこと、特開平７−２５２２６６号公
報及び特開平１０−１３５１５４号公報に示された銅+1
ａｔｍｓ・ｈｆａｃ、並びに特開平１０−１９５６５４
号公報に示された銅プリカーサ化合物では、いずれもス
パッタリング法に代表される物理蒸着法に比べて成膜速
度が遅く、下地膜との密着性に劣る欠点があった。However, copper +1 tmvs
Hfac as well as copper +1 disclosed in JP-A-7-252266 and JP-A-10-135154.
atms-hfac and JP-A-10-195654
Each of the copper precursor compounds disclosed in the above publication has a disadvantage that the film formation rate is slower than that of a physical vapor deposition method represented by a sputtering method, and the adhesion to a base film is poor.
【０００５】本発明の目的は、成膜前の保存状態で分解
しにくく寿命が長い有機金属化学蒸着用の銅薄膜形成用
溶液原料を提供することにある。本発明の別の目的は、
より高い成膜速度が得られ、基板上で効率よく分解して
揮発性が高く、下地膜との密着性に優れた有機金属化学
蒸着用の銅薄膜形成用溶液原料を提供することにある。
本発明の更に別の目的は、下地膜と堅牢に密着する高純
度の銅薄膜を提供することにある。An object of the present invention is to provide a solution material for forming a copper thin film for metal organic chemical vapor deposition which is hardly decomposed in a storage state before film formation and has a long life. Another object of the invention is
It is an object of the present invention to provide a copper thin film forming solution raw material for metal organic chemical vapor deposition, which can obtain a higher film forming rate, is efficiently decomposed on a substrate, has high volatility, and has excellent adhesion to a base film.
Still another object of the present invention is to provide a high-purity copper thin film which is firmly adhered to an underlayer.
【０００６】[0006]
【課題を解決するための手段】請求項１に係る発明は、
次の式（１）で示される銅+1(アリルアルコキシシラン)
(ヘキサフルオロアセチルアセトン)であって、Ｒ1、Ｒ2
及びＲ3がメチル基、エチル基、プロピル基及びブチル
基からなる群より選ばれたアルキル基であることを特徴
とする有機金属化学蒸着用有機銅化合物である。The invention according to claim 1 is
Copper +1 (allylalkoxysilane) represented by the following formula (1)
(Hexafluoroacetylacetone), wherein R 1 , R 2
And R 3 is an alkyl group selected from the group consisting of a methyl group, an ethyl group, a propyl group, and a butyl group.
【０００７】[0007]
【化５】 Embedded image
【０００８】請求項２に係る発明は、請求項１記載の有
機金属化学蒸着用有機銅化合物からなる銅薄膜形成用溶
液原料である。請求項１に係る有機銅化合物からなる銅
薄膜形成用溶液原料は、構造的に式（１）の破線で囲ん
だアリル基のＣＨ2がＳｉとＣＨの間に位置するため、
第一に有機銅化合物の分子鎖が立体的により一層折れ曲
り、成膜時にＣｕ原子が基板に近づき易くなり、下地膜
との密着性が高まるとともに成膜速度がより一層向上す
る。第二にシラン基からの電子供与能に加えて、アリル
基の二重結合のＣ原子へのＣＨ2（破線で囲んだ部分）
の押出し効果により、Ｃｕ原子近傍のＨ原子が電子を供
与するため、Ｃｕのπ結合を補強し、成膜前の有機銅化
合物はその分解が抑制され、長い寿命を有する。一方、
上記Ｃｕ原子近傍のＨ原子の電子供与はそれほど大きく
ないため、成膜中には有機銅化合物は基板上で効率よく
分解して、有機物が揮発する。According to a second aspect of the present invention, there is provided a solution raw material for forming a copper thin film comprising the organocopper compound for an organometallic chemical vapor deposition according to the first aspect. In the solution raw material for forming a copper thin film comprising the organocopper compound according to claim 1, since CH 2 of the allyl group surrounded by the broken line in the formula (1) is structurally located between Si and CH,
First, the molecular chain of the organic copper compound is bent more three-dimensionally, and Cu atoms are more likely to approach the substrate during film formation, whereby the adhesion to the underlying film is increased and the film formation speed is further improved. Secondly, in addition to the electron donating ability from the silane group, CH 2 to the C atom of the double bond of the allyl group (portion enclosed by the broken line)
Due to the extrusion effect, H atoms in the vicinity of Cu atoms donate electrons, so that the π bond of Cu is reinforced, and the organic copper compound before film formation is suppressed from being decomposed, and has a long life. on the other hand,
Since the electron donation of the H atom near the Cu atom is not so large, the organic copper compound is efficiently decomposed on the substrate during the film formation, and the organic substance is volatilized.
【０００９】請求項３に係る発明は、次の式（２）で示
される銅+1(アリルトリメチルシラン)(ヘキサフルオロ
アセチルアセトン)（以下、「銅+1ａｔｍｓ・ｈｆａ
ｃ」の略語で示す。）に請求項１記載の有機金属化学蒸
着用有機銅化合物を添加して銅+1ａｔｍｓ・ｈｆａｃを
溶解してなる銅薄膜形成用溶液原料である。[0009] The invention according to claim 3, copper represented by the following formula (2) +1 (allyltrimethylsilane) (hexafluoroacetylacetone) (hereinafter, "copper +1 atms · hfa
c ". ) Is a solution raw material for forming a copper thin film obtained by adding an organic copper compound for metal organic chemical vapor deposition according to claim 1 to dissolve copper +1 atms · hfac.
【００１０】[0010]
【化６】 Embedded image
【００１１】請求項６に係る発明は、次の式（３）で示
される銅+1(トリメチルビニルシラン)(ヘキサフルオロ
アセチルアセトン)（以下、「銅+1ｔｍｖｓ・ｈｆａ
ｃ」の略語で示す。）に請求項１記載の有機金属化学蒸
着用有機銅化合物を添加して銅+1ｔｍｖｓ・ｈｆａｃを
溶解してなる銅薄膜形成用溶液原料である。According to a sixth aspect of the present invention, there is provided a method for producing copper + 1 (trimethylvinylsilane) (hexafluoroacetylacetone) represented by the following formula (3) (hereinafter referred to as “copper + 1 tmvs · hfa”).
c ". ) Is a solution raw material for forming a copper thin film obtained by dissolving copper +1 tmvs · hfac by adding the organic copper compound for organometallic chemical vapor deposition according to claim 1 to (1).
【００１２】[0012]
【化７】 Embedded image
【００１３】請求項９に係る発明は、次の式（４）で示
される銅+1(トリメトキシビニルシラン)(ヘキサフルオ
ロアセチルアセトン)（以下、「銅+1ｔｍｏｖｓ・ｈｆ
ａｃ」の略語で示す。）に請求項１記載の有機金属化学
蒸着用有機銅化合物０．０１〜２０重量％を添加して銅
+1ｔｍｏｖｓ・ｈｆａｃを溶解してなる銅薄膜形成用溶
液原料である。According to a ninth aspect of the present invention, there is provided a method for producing copper +1 (trimethoxyvinylsilane) (hexafluoroacetylacetone) (hereinafter referred to as "copper +1 tmovs.hf") represented by the following formula (4).
ac ". ) By adding 0.01 to 20% by weight of an organocopper compound for metalorganic chemical vapor deposition according to claim 1;
+1 tmovs · hfac is a solution raw material for forming a copper thin film.
【００１４】[0014]
【化８】 Embedded image
【００１５】請求項３、請求項６又は請求項９に係る発
明では、請求項１記載の有機金属化学蒸着用有機銅化合
物を溶剤として、銅+1ａｔｍｓ・ｈｆａｃ、銅+1ｔｍｖ
ｓ・ｈｆａｃ又は銅+1ｔｍｏｖｓ・ｈｆａｃを溶解する
ことにより、成膜初期に銅+1ａｔｍｓ・ｈｆａｃ、銅+1
ｔｍｖｓ・ｈｆａｃ又は銅+1ｔｍｏｖｓ・ｈｆａｃが分
解し易く、これにより下地膜での初期の銅成長が起り易
くなり、銅薄膜の成長速度が増大する。According to a third, sixth or ninth aspect of the present invention, the organic copper compound for metalorganic chemical vapor deposition according to the first aspect is used as a solvent for copper +1 atms.hfac and copper +1 tmv.
By dissolving s · hfac or copper + 1 tmovs · hfac, copper + 1 atms · hfac, copper + 1
tmvs · hfac or copper + 1 tmmovs · hfac is easily decomposed, whereby initial copper growth on the underlayer is likely to occur, and the growth rate of the copper thin film is increased.
【００１６】請求項５、請求項８又は請求項１１に係る
発明は、銅+1ａｔｍｓ・ｈｆａｃ、銅+1ｔｍｖｓ・ｈｆ
ａｃ又は銅+1ｔｍｏｖｓ・ｈｆａｃに請求項１記載の有
機金属化学蒸着用有機銅化合物０．０１〜２０重量％
と、アリルトリメチルシラン（以下、「ａｔｍｓ」の略
語で示す。）、トリメチルビニルシラン（以下、「ｔｍ
ｖｓ」の略語で示す。）、トリメトキシビニルシラン
（以下、「ｔｍｏｖｓ」の略語で示す。）及びアリルト
リメトキシシラン（以下、「ａｔｍｏｓ」の略語で示
す。）からなる群より選ばれた１種又は２種以上の化合
物０．０１〜４０重量％とを添加して銅+1ａｔｍｓ・ｈ
ｆａｃ、銅+1ｔｍｖｓ・ｈｆａｃ又は銅+1ｔｍｏｖｓ・
ｈｆａｃを溶解してなる銅薄膜形成用溶液原料である。
請求項５、請求項８又は請求項１１に係る発明では、更
にａｔｍｓ、ｔｍｖｓ、ｔｍｏｖｓ、ａｔｍｏｓのうち
少なくとも１種を加えることにより、ａｔｍｓ等におけ
る炭素二重結合が溶液中に増加し、Ｃｕのπ結合が高ま
り、成膜前の保存状態で有機銅化合物の分解が抑制さ
れ、長い寿命の溶液となる。The invention according to claim 5, 8 or 11 is characterized in that copper +1 atms.hfac and copper +1 tmvs.hf
2. The organic copper compound for metalorganic chemical vapor deposition according to claim 1, wherein ac or copper +1 tmovs · hfac is 0.01 to 20% by weight.
And allyltrimethylsilane (hereinafter abbreviated as “atms”), trimethylvinylsilane (hereinafter “tm”
vs ". ), Trimethoxyvinylsilane (hereinafter abbreviated as “tmoves”) and allyltrimethoxysilane (hereinafter abbreviated as “atmos”), one or more compounds 0 selected from the group consisting of .01 to 40% by weight and copper +1 atms.h
fac, copper +1 tmvs · hfac or copper +1 tmovs.
This is a copper thin film forming solution raw material obtained by dissolving hfac.
In the invention according to claim 5, claim 8, or claim 11, by further adding at least one of atms, tmvs, tmovs, and atmos, carbon double bonds in atms and the like increase in the solution, and Cu The π bond is increased, and the decomposition of the organocopper compound is suppressed in a storage state before film formation, resulting in a long-life solution.
【００１７】[0017]
【発明の実施の形態】本発明の有機金属化学蒸着用の銅
薄膜形成用溶液原料は、前述した式（１）に示される銅
+1(アリルアルコキシシラン)(ヘキサフルオロアセチル
アセトン)単体からなるか、或いはこの有機銅化合物を
溶剤として用いて、ベースとなる別の一価の銅金属を含
む有機銅化合物を溶解することにより調製される。更に
本発明の有機金属化学蒸着用の銅薄膜形成用溶液原料
は、請求項１２又は１３に記載するように、ベースとな
る有機銅化合物（銅+1ａｔｍｓ・ｈｆａｃ）に溶剤とし
て銅+1ｔｍｏｖｓ・ｈｆａｃ又は銅+1ｔｍｖｓ・ｈｆａ
ｃを添加して銅+1ａｔｍｓ・ｈｆａｃを溶解することに
より調製される。DETAILED DESCRIPTION OF THE INVENTION The solution raw material for forming a copper thin film for metalorganic chemical vapor deposition according to the present invention is a copper material represented by the aforementioned formula (1).
+1 (allylalkoxysilane) (hexafluoroacetylacetone) alone or prepared by dissolving another organic copper compound containing monovalent copper metal as a base using this organic copper compound as a solvent. You. Further, the solution raw material for forming a copper thin film for metalorganic chemical vapor deposition according to the present invention comprises a base organic copper compound (copper +1 atms.hfac) as a solvent and copper +1 tmovs as a solvent.・ Hfac or copper +1 tmvs ・ hfa
It is prepared by adding c and dissolving copper +1 atms.hfac.
【００１８】式（１）に示される銅+1(アリルアルコキ
シシラン)(ヘキサフルオロアセチルアセトン)におい
て、Ｒ1、Ｒ2及びＲ3はメチル基、エチル基、プロピル
基及びブチル基からなる群より選ばれたアルキル基であ
る。その具体例を表１及び式（５）〜式（１２）に示
す。なお、式（９）及び式（１０）中のＣ4Ｈ9は直鎖状
のアルキル基又は分岐状のアルキル基のいずれであって
もよい。In the copper +1 (allylalkoxysilane) (hexafluoroacetylacetone) represented by the formula (1), R 1 , R 2 and R 3 are selected from the group consisting of methyl, ethyl, propyl and butyl. Alkyl group. Specific examples are shown in Table 1 and Expressions (5) to (12). C 4 H 9 in the formulas (9) and (10) may be either a linear alkyl group or a branched alkyl group.
【００１９】[0019]
【表１】 [Table 1]
【００２０】[0020]
【化９】 Embedded image
【００２１】[0021]
【化１０】 Embedded image
【００２２】[0022]
【化１１】 Embedded image
【００２３】[0023]
【化１２】 Embedded image
【００２４】[0024]
【化１３】 Embedded image
【００２５】[0025]
【化１４】 Embedded image
【００２６】[0026]
【化１５】 Embedded image
【００２７】[0027]
【化１６】 Embedded image
【００２８】上記以外にベースとなる一価の銅金属を含
む有機銅化合物を溶解する溶剤として、式（１３）に示
される一価の銅金属を含む有機銅化合物が挙げられる。
式（１３）において、Ｌの詳細は表２に示される。In addition to the above, examples of the solvent for dissolving the base organic copper compound containing a monovalent copper metal include an organic copper compound containing a monovalent copper metal represented by the following formula (13).
In the equation (13), details of L are shown in Table 2.
【００２９】[0029]
【化１７】 Embedded image
【００３０】[0030]
【表２】 [Table 2]
【００３１】上記溶剤に溶解されるベースとなる一価の
銅金属を含む有機銅化合物としては、請求項３及び請求
項１２に記載された前述した式（２）で示される銅+1ａ
ｔｍｓ・ｈｆａｃ、請求項６に記載された前述した式
（３）で示される銅+1ｔｍｖｓ・ｈｆａｃ、又は請求項
９に記載された前述した式（４）で示される銅+1ｔｍｏ
ｖｓ・ｈｆａｃが挙げられる。上記溶剤の添加量は、銅
+1ａｔｍｓ・ｈｆａｃ、銅+1ｔｍｖｓ・ｈｆａｃ、又は
銅+1ｔｍｏｖｓ・ｈｆａｃ１００重量％に対して０．０
１〜２０重量％であることが好ましい。０．０１重量％
未満では上記溶剤を添加した効果が現れず、銅薄膜の成
長速度は向上しない。また２０重量％を超えると、銅薄
膜中の不純物濃度が高くなり、薄膜の品質を劣化し易く
なり、銅薄膜の成長速度もそれ程向上しない。上記溶剤
の添加量は２〜１０重量％であることが更に好ましい。Examples of the organocopper compounds include copper metal monovalent to be a base which is soluble in the solvent, copper +1 a formula (2) described above are set forth in claims 3 and 12
tms · hfac, copper +1 tmo of formula (4) described above are described copper +1 tmvs · hfac or claim 9, represented by the formula (3) described above according to claim 6
vs. hfac. The amount of the solvent added is copper
0.0 with respect to 100% by weight of +1 atms · hfac, copper +1 tmvs · hfac, or copper +1 tmmovs · hfac.
Preferably it is 1 to 20% by weight. 0.01% by weight
If it is less than the above, the effect of adding the above-mentioned solvent does not appear, and the growth rate of the copper thin film does not improve. On the other hand, when the content exceeds 20% by weight, the impurity concentration in the copper thin film becomes high, the quality of the thin film is easily deteriorated, and the growth rate of the copper thin film is not so improved. The addition amount of the above solvent is more preferably 2 to 10% by weight.
【００３２】また請求項５、請求項８、請求項１１及び
請求項１３に記載したａｔｍｓ、ｔｍｖｓ、ｔｍｏｖ
ｓ、ａｔｍｏｓは助剤として用いられ、この助剤の添加
量は、銅+1ａｔｍｓ・ｈｆａｃ、銅+1ｔｍｖｓ・ｈｆａ
ｃ、又は銅+1ｔｍｏｖｓ・ｈｆａｃ１００重量％に対し
て０．０１〜４０重量％であることが好ましい。この助
剤の添加量が０．０１重量％未満ではａｔｍｓ、ｔｍｖ
ｓ、ｔｍｏｖｓ、ａｔｍｏｓを添加した効果が現れず、
また４０重量％を超えると、銅薄膜中の不純物濃度が高
くなり、薄膜の品質を劣化し易くなり、銅薄膜の成長速
度もそれ程向上しない。上記助剤の添加量は２〜１０重
量％であることが更に好ましい。請求項２ないし１３い
ずれかに係る発明の銅薄膜形成用溶液原料により形成さ
れた銅薄膜は、下地膜と堅牢に密着し、高純度である特
長を有する。この銅薄膜は、例えばシリコン基板表面の
ＳｉＯ2膜上にスパッタリング法又はＭＯＣＶＤ法によ
り形成されたＴｉＮ膜又はＴａＮ膜上にＭＯＣＶＤ法に
より形成される。Atms, tmvs, tmov described in claim 5, claim 8, claim 11, and claim 13
s and atmos are used as auxiliaries, and the amount of the auxiliaries is copper +1 atms · hfac, copper +1 tmvs · hfa
The content is preferably 0.01 to 40% by weight based on 100% by weight of c or copper + 1 tmovs · hfac. If the amount of the auxiliary agent is less than 0.01% by weight, atms, tmv
The effect of adding s, tmovs and atmos does not appear,
On the other hand, if the content exceeds 40% by weight, the impurity concentration in the copper thin film increases, the quality of the thin film tends to deteriorate, and the growth rate of the copper thin film does not increase so much. It is more preferable that the amount of the auxiliary added is 2 to 10% by weight. The copper thin film formed from the copper thin film forming solution raw material according to any one of the second to thirteenth aspects has the feature that it adheres firmly to the underlying film and has high purity. This copper thin film is formed by a MOCVD method on a TiN film or a TaN film formed by, for example, a sputtering method or a MOCVD method on a SiO 2 film on a silicon substrate surface.
【００３３】なお、本発明の基板はその種類を特に限定
されるものではない。また、本明細書では、一価の銅金
属を含む有機銅化合物を構成する化合物を慣用的に「銅
+1(アリルトリメチルシラン)(ヘキサフルオロアセチル
アセトン)」と表記しているが、これは正式には「銅
+1(３−トリメチルシリル−１−プロペン)(１，１，
１，５，５，５−ヘキサフルオロ−２，４−ペンタンジ
オネート)」と表記される。また「銅+1(トリメチルビニ
ルシラン)(ヘキサフルオロアセチルアセトン)」は正式
には「銅+1(トリメチルシリル−１−エチン)(１，１，
１，５，５，５−ヘキサフルオロ−２，４−ペンタンジ
オネート)」と表記され、更に「銅+1(トリメトキシビニ
ルシラン)(ヘキサフルオロアセチルアセトン)」は正式
には「銅+1(トリメトキシシリル−１−エチン)(１，
１，１，５，５，５−ヘキサフルオロ−２，４−ペンタ
ンジオネート)」と表記される。The type of the substrate of the present invention is not particularly limited. Further, in the present specification, a compound constituting an organic copper compound containing a monovalent copper metal is conventionally referred to as “copper
+1 (allyltrimethylsilane) (hexafluoroacetylacetone), which is formally
+1 (3-trimethylsilyl-1-propene) (1,1,
1,5,5,5-hexafluoro-2,4-pentanedionate) ". Also, “copper + 1 (trimethylvinylsilane) (hexafluoroacetylacetone)” is formally referred to as “copper + 1 (trimethylsilyl-1-ethyne) (1,1,
1,5,5,5-hexafluoro-2,4-pentanedionate), and “copper + 1 (trimethoxyvinylsilane) (hexafluoroacetylacetone)” is formally referred to as “copper + 1 (tri (Methoxysilyl-1-ethyne) (1,
1,1,5,5,5-hexafluoro-2,4-pentanedionate) ".
【００３４】[0034]
【実施例】次に本発明の実施例を比較例とともに説明す
る。 ＜実施例１＞前述した式（５）に示した銅+1ａｔｍｏｓ
・ｈｆａｃからなる有機銅化合物を銅薄膜形成用溶液原
料として用意した。この有機銅化合物は次の方法により
合成した。酸化銅(I)１３．０ｇに十分に窒素脱気を行
った乾燥塩化メチレン１５０ｍｌを注ぎ、懸濁液とし
た。アルリトリメトキシシラン（ａｔｍｏｓ）６．９２
ｇを激しく攪拌しながら添加し、更に１，１，１，５，
５，５−ヘキサフルオロ−２，４−ペンタンジオン１
２．６ｇを１滴ずつ滴下ロートより滴下した。反応系を
４時間攪拌した後、窒素気流下でろ過し、ろ液を３５℃
の減圧下で留去し、濃緑色の液体を得た。この液体をカ
ラムクロマトグラフィーにより精製し、明黄色の液体で
ある前述した式（５）で示される、銅+1(アリルトリメ
トキシシラン)(１，１，１，５，５，５−ヘキサフルオ
ロ−２，４−ペンタンジオネート)を１６．７ｇ得た。
得られた有機銅化合物の同定は、ＮＭＲ及び元素分析に
より行った。Next, examples of the present invention will be described together with comparative examples. <Embodiment 1> Copper +1 atmos shown in the above equation (5)
-An organic copper compound comprising hfac was prepared as a solution raw material for forming a copper thin film. This organic copper compound was synthesized by the following method. 150 ml of dry methylene chloride sufficiently deaerated with nitrogen was poured into 13.0 g of copper (I) oxide to form a suspension. Allitrimethoxysilane (atmos) 6.92
g with vigorous stirring.
5,5-hexafluoro-2,4-pentanedione 1
2.6 g was dropped from the dropping funnel drop by drop. After stirring the reaction system for 4 hours, the mixture was filtered under a nitrogen stream, and the filtrate was heated at 35 ° C.
Under reduced pressure to obtain a dark green liquid. This liquid was purified by column chromatography, and copper + 1 (allyltrimethoxysilane) (1,1,1,5,5,5-hexafluoro) represented by the above formula (5), which was a light yellow liquid, was obtained. 16.7 g of (-2,4-pentanedionate) was obtained.
The obtained organic copper compound was identified by NMR and elemental analysis.
【００３５】ＮＭＲ分析の結果は、１Ｈ−ＮＭＲ（ＣＤ
ＣＬ３）；δ０．０８（ｓ，９Ｈ），１．６１（ｄ，２
Ｈ，Ｊ＝７．８２Ｈｚ），４．３４（ｍ，２Ｈ），５．
４５（ｍ，１Ｈ），６．０８（ｓ，１Ｈ）であり、また
元素分析の結果は、Ｃ３２．５％、Ｈ３．７２％、Ｏ１
９．６％、Ｆ２８．２％、Ｃｕ１５．５％（理論値Ｃ３
２．６％、Ｈ３．７１％、Ｏ１９．７％、Ｆ２８．１
％、Ｃｕ１５．６％）であった。The result of the NMR analysis was 1H-NMR (CD
CL3); δ 0.08 (s, 9H), 1.61 (d, 2
H, J = 7.82 Hz), 4.34 (m, 2H), 5.
45 (m, 1H) and 6.08 (s, 1H). The results of elemental analysis were as follows: C 32.5%, H 3.72%, O1
9.6%, F28.2%, Cu 15.5% (theoretical value C3
2.6%, H 3.71%, O 19.7%, F28.1
%, Cu 15.6%).
【００３６】この有機銅化合物からなる銅薄膜形成用溶
液原料を３ヶ月間容器に密閉して保管した後、容器から
取出して用い、ＭＯＣＶＤ法により銅薄膜を成膜した。
基板として、基板表面のＳｉＯ2膜（厚さ５０００Å）
上にスパッタリング法によりＴｉＮ膜（厚さ５０ｎｍ）
を形成したシリコン基板を用い、基板温度を１５０℃、
１６０℃、１７０℃、１８０℃、１９０℃、２００℃、
２１０℃の７段階に変えた。気化温度を７０℃、圧力を
２ｔｏｒｒにそれぞれ設定した。キャリアガスとしてＡ
ｒガスを用い、その流量を１００ｃｃｍとした。銅薄膜
形成用溶液原料を０．２ｃｃ／分の割合で５分間供給
し、その膜厚を膜の断面ＳＥＭ像から測定した。表３に
上記時間内における最高の膜厚を単位時間当りに換算し
て示す。また四探針式比抵抗測定装置により膜の比抵抗
値を、電子線表面粗さ解析装置（エリオニクス社製、Ｅ
ＲＡ−８０００）により膜の表面粗さをそれぞれ測定し
た。表面粗さは表面の最上部と最下部の差をいう。これ
らの結果を表３に示す。The solution raw material for forming a copper thin film composed of this organic copper compound was sealed in a container for 3 months and stored, then taken out from the container and used to form a copper thin film by MOCVD.
As substrate, SiO 2 film on substrate surface (thickness 5000 mm)
TiN film (50 nm thick) by sputtering
Using a silicon substrate formed with a substrate temperature of 150 ° C.
160 ° C, 170 ° C, 180 ° C, 190 ° C, 200 ° C,
The temperature was changed to seven stages at 210 ° C. The vaporization temperature was set at 70 ° C., and the pressure was set at 2 torr. A as carrier gas
The flow rate was set to 100 ccm using r gas. The solution raw material for forming a copper thin film was supplied at a rate of 0.2 cc / min for 5 minutes, and the film thickness was measured from a cross-sectional SEM image of the film. Table 3 shows the maximum film thickness in the above-mentioned time in terms of unit time. Further, the specific resistance of the film was measured by a four-probe type specific resistance measuring device, and the surface roughness of the film was analyzed by an electron beam surface roughness analyzer (Elionix, E.
RA-8000) to measure the surface roughness of the film. Surface roughness refers to the difference between the top and bottom of the surface. Table 3 shows the results.
【００３７】＜実施例２＞前述した式（６）に示される
銅+1ａｔｅｏｓ・ｈｆａｃからなる有機銅化合物を銅薄
膜形成用溶液原料として用意した。この有機銅化合物は
次の方法により合成した。実施例１と同様に酸化銅(I)
１３．０ｇに十分に窒素脱気を行った乾燥塩化メチレン
１５０ｍｌを注ぎ、懸濁液とした。アルリトリエトキシ
シラン（ａｔｅｏｓ）５．８４ｇを激しく攪拌しながら
添加し、更に１，１，１，５，５，５−ヘキサフルオロ
−２，４−ペンタンジオン１２．６ｇを１滴ずつ滴下ロ
ートより滴下した。反応系を４時間攪拌した後、窒素気
流下でろ過し、ろ液を３５℃の減圧下で留去し、濃緑色
の液体を得た。この液体をカラムクロマトグラフィーに
より精製し、明黄色の液体である前述した式（６）で示
される、銅+1(アリルトリエトキシシラン)(１，１，
１，５，５，５−ヘキサフルオロ−２，４−ペンタンジ
オネート)を１３．５ｇ得た。得られた有機銅化合物の
同定は、ＮＭＲ及び元素分析により行った。<Example 2> An organic copper compound represented by the above-mentioned formula (6) and comprising copper + 1 ateos.hfac was prepared as a solution raw material for forming a copper thin film. This organic copper compound was synthesized by the following method. Copper (I) oxide as in Example 1
150 ml of dry methylene chloride sufficiently degassed with nitrogen was poured into 13.0 g to form a suspension. 5.84 g of alritriethoxysilane (ateos) was added with vigorous stirring, and 12.6 g of 1,1,1,5,5,5-hexafluoro-2,4-pentanedione was further added dropwise from the dropping funnel. It was dropped. After stirring the reaction system for 4 hours, the mixture was filtered under a nitrogen stream, and the filtrate was distilled off under reduced pressure at 35 ° C. to obtain a dark green liquid. This liquid was purified by column chromatography, and copper + 1 (allyltriethoxysilane) (1,1,
1,5,5,5-hexafluoro-2,4-pentanedionate) was obtained in an amount of 13.5 g. The obtained organic copper compound was identified by NMR and elemental analysis.
【００３８】ＮＭＲ分析；１Ｈ−ＮＭＲ（ＣＤＣＬ
３）；δ２．０６３（ｄ，９Ｈ），１．８６（ｑ，６
Ｈ），１．６１（ｄ，２Ｈ，Ｊ＝７．９２Ｈｚ），４．
３５（ｍ，２Ｈ），５．５２（ｍ，１Ｈ），６．１２
（ｓ，１Ｈ）、及び元素分析；Ｃ３７．５％、Ｈ４．７
２％、Ｏ１７．８％、Ｆ２５．５％、Ｃｕ１４．２％
（理論値Ｃ３７．６％、Ｈ４．７０％、Ｏ１７．９％、
Ｆ２５．５％、Ｃｕ１４．２％）を得た。この有機銅化
合物からなる銅薄膜形成用溶液原料を３ヶ月間容器に密
閉して保管した後、容器から取出して用い、実施例１と
同一の条件でＭＯＣＶＤ法により銅薄膜を成膜した。膜
厚、比抵抗値、表面粗さも実施例と同様にして測定し
た。これらの結果を表３に示す。NMR analysis; 1H-NMR (CDCL
3); δ 2.063 (d, 9H), 1.86 (q, 6
H), 1.61 (d, 2H, J = 7.92 Hz), 4.
35 (m, 2H), 5.52 (m, 1H), 6.12
(S, 1H), and elemental analysis; C37.5%, H4.7
2%, O17.8%, F25.5%, Cu 14.2%
(Theoretical value C37.6%, H4.70%, O17.9%,
F25.5%, Cu 14.2%). The copper thin film forming solution raw material comprising the organic copper compound was sealed and stored in a container for 3 months, then taken out of the container and used, and a copper thin film was formed by MOCVD under the same conditions as in Example 1. The film thickness, specific resistance, and surface roughness were also measured in the same manner as in the examples. Table 3 shows the results.
【００３９】[0039]
【表３】 [Table 3]
【００４０】表３から明らかなように、実施例１及び実
施例２とも基板温度が１６０〜２００℃の範囲、特に１
８０〜２００℃の範囲では、銅薄膜の成長速度が大き
く、１分間で成長した膜厚が４００ｎｍ前後になった。
また実施例１及び実施例２とも基板温度によらず、膜の
比抵抗値は理論値１．６μΩｃｍに対して１．５〜１．
８μΩｃｍであり、表面粗さは平均０．９８ｎｍであっ
た。As is apparent from Table 3, the substrate temperatures in Examples 1 and 2 were in the range of 160 to 200 ° C.
In the range of 80 to 200 ° C., the growth rate of the copper thin film was high, and the film thickness grown in one minute was about 400 nm.
In both the first and second embodiments, the specific resistance of the film is 1.5 to 1.15 with respect to the theoretical value of 1.6 μΩcm regardless of the substrate temperature.
The average surface roughness was 0.98 nm.
【００４１】＜実施例３＞前述した式（２）で示される
銅+1ａｔｍｓ・ｈｆａｃに実施例１の有機銅化合物又は
実施例２の有機銅化合物を溶剤として用い、この溶剤を
表４に示す割合で添加して銅薄膜形成用溶液原料を調製
した。この原料を３ヶ月間容器に密閉して保管した後、
容器から取出して用い、基板温度を１８０℃に統一した
以外、実施例１と同一の条件でＭＯＣＶＤ法により銅薄
膜を成膜した。膜厚、比抵抗値、表面粗さも実施例と同
様にして測定した。これらの結果を表４に示す。<Example 3> The organic copper compound of Example 1 or the organic copper compound of Example 2 was used as a solvent for the copper +1 atms.hfac represented by the above formula (2), and the solvent is shown in Table 4. A solution raw material for forming a copper thin film was prepared by adding at the indicated ratio. After keeping this raw material sealed in a container for 3 months,
A copper thin film was formed by the MOCVD method under the same conditions as in Example 1 except that the substrate was used out of the container and the substrate temperature was unified to 180 ° C. The film thickness, specific resistance, and surface roughness were also measured in the same manner as in the examples. Table 4 shows the results.
【００４２】[0042]
【表４】 [Table 4]
【００４３】表４から明らかなように、溶剤の添加量が
０．０１〜２０重量％の範囲で１分間で成長した膜厚が
４４０〜５６０ｎｍと大きかったのに対して、この範囲
外では２００ｎｍ台であった。全体的に、膜の比抵抗値
は理論値１．６μΩｃｍに対して１．５〜１．８μΩｃ
ｍであり、表面粗さは平均０．９５ｎｍであった。As is apparent from Table 4, the film thickness grown in one minute was as large as 440 to 560 nm when the amount of the solvent added was in the range of 0.01 to 20% by weight. It was a stand. Overall, the resistivity of the film is 1.5-1.8 μΩc for a theoretical value of 1.6 μΩcm.
m, and the average surface roughness was 0.95 nm.
【００４４】＜実施例４＞前述した式（２）で示される
銅+1ａｔｍｓ・ｈｆａｃに実施例１の有機銅化合物又は
実施例２の有機銅化合物を溶剤として用い、この溶剤を
５重量％添加した後、更にアリルトリメチルシラン（ａ
ｔｍｓ）又はトリメチルビニルシラン（ｔｍｖｓ）を助
剤として用い、この助剤を表５に示す割合で添加して銅
薄膜形成用溶液原料を調製した。この原料を３ヶ月間容
器に密閉して保管した後、容器から取出して用い、基板
温度を１８０℃に統一した以外、実施例１と同一条件で
ＭＯＣＶＤ法により銅薄膜を成膜した。膜厚、比抵抗
値、表面粗さも実施例と同様にして測定した。これらの
結果を表５に示す。Example 4 The organic copper compound of Example 1 or the organic copper compound of Example 2 was used as a solvent for copper +1 atms.hfac represented by the above formula (2), and this solvent was used in an amount of 5% by weight. After the addition, allyltrimethylsilane (a
tms) or trimethylvinylsilane (tmvs) as an auxiliary, and the auxiliary was added at the ratio shown in Table 5 to prepare a copper thin film forming solution raw material. The raw material was sealed and stored in a container for 3 months, taken out of the container and used, and a copper thin film was formed by MOCVD under the same conditions as in Example 1 except that the substrate temperature was unified to 180 ° C. The film thickness, specific resistance, and surface roughness were also measured in the same manner as in the examples. Table 5 shows the results.
【００４５】[0045]
【表５】 [Table 5]
【００４６】表５から明らかなように、助剤の添加量が
０．０１重量％以上で１分間で成長した膜厚が４６０〜
７１０ｎｍと大きかったのに対して、０．０１重量％未
満及び４０重量％を超えると３００ｎｍ台であった。全
体的に、膜の比抵抗値は理論値１．６μΩｃｍに対して
１．５〜１．８μΩｃｍであり、表面粗さは平均０．９
４ｎｍであった。As is clear from Table 5, when the amount of the auxiliary added was 0.01% by weight or more, the film thickness grown in one minute was 460-600.
While it was as large as 710 nm, it was on the order of 300 nm when less than 0.01% by weight and more than 40% by weight. Overall, the specific resistance value of the film is 1.5 to 1.8 μΩcm with respect to the theoretical value of 1.6 μΩcm, and the surface roughness averages 0.9 μΩcm.
4 nm.
【００４７】＜実施例５＞前述した式（２）で示される
銅+1ａｔｍｓ・ｈｆａｃに実施例１の有機銅化合物又は
実施例２の有機銅化合物を溶剤として用い、この溶剤を
５重量％添加した後、更にアリルトリメトキシシラン
（ａｔｍｏｓ）又はトリメトキシビニルシラン（ｔｍｏ
ｖｓ）を助剤として用い、この助剤を表６に示す割合で
添加して銅薄膜形成用溶液原料を調製した。この原料を
３ヶ月間容器に密閉して保管した後、容器から取出して
用い、基板温度を１８０℃に統一した以外、実施例１と
同一条件でＭＯＣＶＤ法により銅薄膜を成膜した。膜
厚、比抵抗値、表面粗さも実施例と同様にして測定し
た。これらの結果を表６に示す。<Example 5> The organic copper compound of Example 1 or the organic copper compound of Example 2 was used as a solvent for copper +1 atms.hfac represented by the above formula (2), and this solvent was used in an amount of 5% by weight. After the addition, allyltrimethoxysilane (atmos) or trimethoxyvinylsilane (tmo)
vs) was used as an auxiliary, and this auxiliary was added at the ratio shown in Table 6 to prepare a copper thin film forming solution raw material. The raw material was sealed and stored in a container for 3 months, taken out of the container and used, and a copper thin film was formed by MOCVD under the same conditions as in Example 1 except that the substrate temperature was unified to 180 ° C. The film thickness, specific resistance, and surface roughness were also measured in the same manner as in the examples. Table 6 shows the results.
【００４８】[0048]
【表６】 [Table 6]
【００４９】表６から明らかなように、助剤の添加量が
０．０１〜１０重量％の範囲で１分間で成長した膜厚が
４６０〜７１０ｎｍと大きかったのに対して、０．０１
重量％未満及び４０重量％を超えると３００ｎｍ台であ
った。全体的に、膜の比抵抗値は理論値１．６μΩｃｍ
に対して１．５〜１．８μΩｃｍであり、表面粗さは平
均０．９２ｎｍであった。As is clear from Table 6, the film thickness grown in one minute was as large as 460 to 710 nm when the amount of the auxiliary agent added was in the range of 0.01 to 10% by weight.
If it was less than 40% by weight or less than 40% by weight, it was on the order of 300 nm. Overall, the resistivity of the film is 1.6 μΩcm theoretical
Was 1.5 to 1.8 μΩcm, and the average surface roughness was 0.92 nm.
【００５０】＜実施例６＞前述した式（３）で示される
銅+1ｔｍｖｓ・ｈｆａｃに実施例１の有機銅化合物又は
実施例２の有機銅化合物を溶剤として用い、この溶剤を
表７に示す割合で添加して銅薄膜形成用溶液原料を調製
した。この原料を３ヶ月間容器に密閉して保管した後、
容器から取出して用い、基板温度を１８０℃に統一した
以外、実施例１と同一の条件でＭＯＣＶＤ法により銅薄
膜を成膜した。膜厚、比抵抗値、表面粗さも実施例と同
様にして測定した。これらの結果を表７に示す。Example 6 The organic copper compound of Example 1 or the organic copper compound of Example 2 was used as a solvent for the copper +1 tmvs · hfac represented by the above formula (3). A solution raw material for forming a copper thin film was prepared by adding at the indicated ratio. After keeping this raw material sealed in a container for 3 months,
A copper thin film was formed by the MOCVD method under the same conditions as in Example 1 except that the substrate was used out of the container and the substrate temperature was unified to 180 ° C. The film thickness, specific resistance, and surface roughness were also measured in the same manner as in the examples. Table 7 shows the results.
【００５１】[0051]
【表７】 [Table 7]
【００５２】表７から明らかなように、実施例１と実施
例２の溶剤の添加量が０．０１〜２０重量％の範囲で１
分間で成長した膜厚が４４０〜５６０ｎｍと大きかった
のに対して、この範囲外では２００ｎｍ台であった。全
体的に、膜の比抵抗値は理論値１．６μΩｃｍに対して
１．５〜１．８μΩｃｍであり、表面粗さは平均０．９
６ｎｍであった。As is clear from Table 7, when the amount of the solvent used in Examples 1 and 2 was 0.01 to 20% by weight, 1
While the film thickness grown in one minute was as large as 440 to 560 nm, it was on the order of 200 nm outside this range. Overall, the specific resistance value of the film is 1.5 to 1.8 μΩcm with respect to the theoretical value of 1.6 μΩcm, and the surface roughness averages 0.9 μΩcm.
6 nm.
【００５３】＜実施例７＞前述した式（３）で示される
銅+1ｔｍｖｓ・ｈｆａｃに実施例１の有機銅化合物又は
実施例２の有機銅化合物を溶剤として用い、この溶剤を
５重量％添加した後、更にアリルトリメチルシラン（ａ
ｔｍｓ）又はトリメチルビニルシラン（ｔｍｖｓ）を助
剤として用い、この助剤を表８に示す割合で添加して銅
薄膜形成用溶液原料を調製した。この原料を３ヶ月間容
器に密閉して保管した後、容器から取出して用い、基板
温度を１８０℃に統一した以外、実施例１と同一条件で
ＭＯＣＶＤ法により銅薄膜を成膜した。膜厚、比抵抗
値、表面粗さも実施例と同様にして測定した。これらの
結果を表８に示す。<Example 7> The organic copper compound of Example 1 or the organic copper compound of Example 2 was used as a solvent for copper +1 tmvs · hfac represented by the above formula (3), and this solvent was used in an amount of 5% by weight. After the addition, allyltrimethylsilane (a
tms) or trimethylvinylsilane (tmvs) as an auxiliary, and the auxiliary was added at the ratio shown in Table 8 to prepare a copper thin film forming solution raw material. The raw material was sealed and stored in a container for 3 months, taken out of the container and used, and a copper thin film was formed by MOCVD under the same conditions as in Example 1 except that the substrate temperature was unified to 180 ° C. The film thickness, specific resistance, and surface roughness were also measured in the same manner as in the examples. Table 8 shows the results.
【００５４】[0054]
【表８】 [Table 8]
【００５５】表８から明らかなように、助剤の添加量が
０．０１重量％以上で１分間で成長した膜厚が３６７〜
７１６ｎｍと大きかったのに対して、０．０１重量％未
満及び４０重量％を超えると３００ｎｍ台であった。全
体的に、膜の比抵抗値は理論値１．６μΩｃｍに対して
１．５〜１．８μΩｃｍであり、表面粗さは平均０．９
６ｎｍであった。As is clear from Table 8, when the amount of the auxiliary agent added was 0.01% by weight or more, the film thickness grown in one minute was 367 to 367%.
While it was as large as 716 nm, it was on the order of 300 nm when it was less than 0.01% by weight and more than 40% by weight. Overall, the specific resistance value of the film is 1.5 to 1.8 μΩcm with respect to the theoretical value of 1.6 μΩcm, and the surface roughness averages 0.9 μΩcm.
6 nm.
【００５６】＜実施例８＞前述した式（３）で示される
銅+1ｔｍｖｓ・ｈｆａｃに実施例１の有機銅化合物又は
実施例２の有機銅化合物を溶剤として用い、この溶剤を
５重量％添加した後、更にアリルトリメトキシシラン
（ａｔｍｏｓ）又はトリメトキシビニルシラン（ｔｍｏ
ｖｓ）を助剤として用い、この助剤を表９に示す割合で
添加して銅薄膜形成用溶液原料を調製した。この原料を
３ヶ月間容器に密閉して保管した後、容器から取出して
用い、基板温度を１８０℃に統一した以外、実施例１と
同一条件でＭＯＣＶＤ法により銅薄膜を成膜した。膜
厚、比抵抗値、表面粗さも実施例と同様にして測定し
た。これらの結果を表９に示す。<Example 8> The organic copper compound of Example 1 or the organic copper compound of Example 2 was used as a solvent for the copper +1 tmvs · hfac represented by the above formula (3), and this solvent was used in an amount of 5% by weight. After the addition, allyltrimethoxysilane (atmos) or trimethoxyvinylsilane (tmo)
vs) was used as an auxiliary, and this auxiliary was added at the ratio shown in Table 9 to prepare a solution raw material for forming a copper thin film. The raw material was sealed and stored in a container for 3 months, taken out of the container and used, and a copper thin film was formed by MOCVD under the same conditions as in Example 1 except that the substrate temperature was unified to 180 ° C. The film thickness, specific resistance, and surface roughness were also measured in the same manner as in the examples. Table 9 shows the results.
【００５７】[0057]
【表９】 [Table 9]
【００５８】表９から明らかなように、助剤の添加量が
０．０１〜１０重量％の範囲で１分間で成長した膜厚が
４６２〜７１０ｎｍと大きかったのに対して、０．０１
重量％未満及び４０重量％を超えると３００ｎｍ台であ
った。全体的に、膜の比抵抗値は理論値１．６μΩｃｍ
に対して１．５〜１．８μΩｃｍであり、表面粗さは平
均０．９７ｎｍであった。As is apparent from Table 9, the film thickness grown in one minute was as large as 462 to 710 nm when the amount of the auxiliary agent was in the range of 0.01 to 10% by weight.
If it was less than 40% by weight or less than 40% by weight, it was on the order of 300 nm. Overall, the resistivity of the film is 1.6 μΩcm theoretical
Was 1.5 to 1.8 μΩcm, and the average surface roughness was 0.97 nm.
【００５９】＜実施例９＞前述した式（２）で示される
銅+1ａｔｍｓ・ｈｆａｃに前述した式（４）に示される
銅+1ｔｍｏｖｓ・ｈｆａｃからなる有機銅化合物又は前
述した式（３）に示される銅+1ｔｍｖｓ・ｈｆａｃから
なる有機銅化合物を溶剤として用い、この溶剤を表１０
に示す割合で添加して銅薄膜形成用溶液原料を調製し
た。この原料を３ヶ月間容器に密閉して保管した後、容
器から取出して用い、基板温度を１８０℃に統一した以
外、実施例１と同一の条件でＭＯＣＶＤ法により銅薄膜
を成膜した。膜厚、比抵抗値、表面粗さも実施例と同様
にして測定した。これらの結果を表１０に示す。[0059] <Example 9> organocopper compound of copper +1 tmovs · hfac represented by formula (4) described above to the copper +1 atms · hfac represented by the aforementioned formula (2) or the aforementioned equation (3 an organic copper compound comprising copper +1 tmvs · hfac shown in) as a solvent, Table 10 the solvent
To prepare a copper thin film forming solution raw material. The raw material was sealed in a container for 3 months and stored, then taken out of the container and used, and a copper thin film was formed by MOCVD under the same conditions as in Example 1 except that the substrate temperature was unified to 180 ° C. The film thickness, specific resistance, and surface roughness were also measured in the same manner as in the examples. Table 10 shows the results.
【００６０】[0060]
【表１０】 [Table 10]
【００６１】表１０から明らかなように、溶剤の添加量
が０．０１〜２０重量％の範囲で１分間で成長した膜厚
が４５０〜５６０ｎｍと大きかったのに対して、この範
囲外では２００ｎｍ台であった。全体的に、膜の比抵抗
値は理論値１．６μΩｃｍに対して１．５〜１．８μΩ
ｃｍであり、表面粗さは平均０．９８ｎｍであった。As is apparent from Table 10, the film thickness grown in one minute was as large as 450 to 560 nm when the amount of the solvent added was in the range of 0.01 to 20% by weight. It was a stand. Overall, the specific resistance of the film is 1.5-1.8 μΩ against a theoretical value of 1.6 μΩcm.
cm, and the surface roughness averaged 0.98 nm.
【００６２】＜実施例１０＞前述した式（２）で示され
る銅+1ａｔｍｓ・ｈｆａｃに前述した式（４）に示され
る銅+1ｔｍｏｖｓ・ｈｆａｃからなる有機銅化合物又は
前述した式（３）に示される銅+1ｔｍｖｓ・ｈｆａｃか
らなる有機銅化合物を溶剤として用い、この溶剤を５重
量％添加した後、更にアリルトリメチルシラン（ａｔｍ
ｓ）又はトリメチルビニルシラン（ｔｍｖｓ）を助剤と
して用い、この助剤を表１１に示す割合で添加して銅薄
膜形成用溶液原料を調製した。この原料を３ヶ月間容器
に密閉して保管した後、容器から取出して用い、基板温
度を１８０℃に統一した以外、実施例１と同一条件でＭ
ＯＣＶＤ法により銅薄膜を成膜した。膜厚、比抵抗値、
表面粗さも実施例と同様にして測定した。これらの結果
を表１１に示す。[0062] <Example 10> organic copper compound comprising copper +1 tmovs · hfac represented by formula (4) described above to the copper +1 atms · hfac represented by the aforementioned formula (2) or the aforementioned equation (3 an organic copper compound comprising copper +1 tmvs · hfac shown in) as a solvent, after the addition of the solvent 5% by weight, further allyltrimethylsilane (atm
s) or trimethylvinylsilane (tmvs) was used as an auxiliary, and this auxiliary was added at the ratio shown in Table 11 to prepare a copper thin film forming solution raw material. This raw material was sealed in a container for 3 months, stored in a container, taken out of the container, and used under the same conditions as in Example 1 except that the substrate temperature was unified to 180 ° C.
A copper thin film was formed by the OCVD method. Film thickness, resistivity,
The surface roughness was measured in the same manner as in the example. Table 11 shows the results.
【００６３】[0063]
【表１１】 [Table 11]
【００６４】表１１から明らかなように、助剤の添加量
が０．０１〜１０重量％の範囲で１分間で成長した膜厚
が４６０〜７１５ｎｍと大きかったのに対して、０．０
１重量％未満及び４０重量％を超えると３００ｎｍ台で
あった。全体的に、膜の比抵抗値は理論値１．６μΩｃ
ｍに対して１．５〜１．８μΩｃｍであり、表面粗さは
平均０．９４ｎｍであった。As is clear from Table 11, the film thickness grown in one minute in the range of 0.01 to 10% by weight of the auxiliary agent was as large as 460 to 715 nm.
If it was less than 1% by weight or more than 40% by weight, the value was on the order of 300 nm. Overall, the resistivity of the film is 1.6 μΩc theoretical.
m was 1.5 to 1.8 μΩcm, and the average surface roughness was 0.94 nm.
【００６５】＜実施例１１＞前述した式（２）で示され
る銅+1ａｔｍｓ・ｈｆａｃに前述した式（４）に示され
る銅+1ｔｍｏｖｓ・ｈｆａｃからなる有機銅化合物又は
前述した式（３）に示される銅+1ｔｍｖｓ・ｈｆａｃか
らなる有機銅化合物を溶剤として用い、この溶剤を５重
量％添加した後、更にアリルトリメトキシシラン（ａｔ
ｍｏｓ）又はトリメトキシビニルシラン（ｔｍｏｖｓ）
を助剤として用い、この助剤を表１２に示す割合で添加
して銅薄膜形成用溶液原料を調製した。この原料を３ヶ
月間容器に密閉して保管した後、容器から取出して用
い、基板温度を１８０℃に統一した以外、実施例１と同
一条件でＭＯＣＶＤ法により銅薄膜を成膜した。膜厚、
比抵抗値、表面粗さも実施例と同様にして測定した。こ
れらの結果を表１２に示す。[0065] <Example 11> organic copper compound comprising copper +1 tmovs · hfac represented by formula (4) described above to the copper +1 atms · hfac represented by the aforementioned formula (2) or the aforementioned equation (3 an organic copper compound comprising copper +1 tmvs · hfac shown in) as a solvent, after the addition of the solvent 5% by weight, further allyl trimethoxysilane (at
mos) or trimethoxyvinylsilane (tmovs)
Was used as an auxiliary agent, and the auxiliary agent was added at the ratio shown in Table 12 to prepare a copper thin film forming solution raw material. The raw material was sealed and stored in a container for 3 months, taken out of the container and used, and a copper thin film was formed by MOCVD under the same conditions as in Example 1 except that the substrate temperature was unified to 180 ° C. Film thickness,
The specific resistance and the surface roughness were also measured in the same manner as in the examples. Table 12 shows the results.
【００６６】[0066]
【表１２】 [Table 12]
【００６７】表１２から明らかなように、助剤の添加量
が０．０１〜１０重量％の範囲で１分間で成長した膜厚
が４６０〜７１０ｎｍと大きかったのに対して、０．０
１重量％未満及び４０重量％を超えると３００ｎｍ台で
あった。全体的に、膜の比抵抗値は理論値１．６μΩｃ
ｍに対して１．５〜１．８μΩｃｍであり、表面粗さは
平均０．９５ｎｍであった。As is clear from Table 12, the film thickness grown in one minute in the range of the additive amount of 0.01 to 10% by weight was as large as 460 to 710 nm.
If it was less than 1% by weight or more than 40% by weight, the value was on the order of 300 nm. Overall, the resistivity of the film is 1.6 μΩc theoretical.
m was 1.5 to 1.8 μΩcm, and the surface roughness was 0.95 nm on average.
【００６８】＜比較例１＞銅+1ａｔｍｓ・ｈｆａｃ単体
からなる３ヶ月保管した銅薄膜形成用溶液原料を用い
て、基板温度を１８０℃にした以外、実施例１と同一条
件でＭＯＣＶＤ法により銅薄膜を成膜した。膜厚、比抵
抗値、表面粗さも実施例と同様にして測定した。これら
の結果を表１３に示す。 ＜比較例２＞銅+1ｔｍｖｓ・ｈｆａｃ単体からなる３ヶ
月保管した銅薄膜形成用溶液原料を用いて、基板温度を
１８０℃にした以外、実施例１と同一条件でＭＯＣＶＤ
法により銅薄膜を成膜した。膜厚、比抵抗値、表面粗さ
も実施例と同様にして測定した。これらの結果を表１３
に示す。Comparative Example 1 A MOCVD method was performed under the same conditions as in Example 1 except that the substrate temperature was set to 180 ° C. using a copper thin film forming solution raw material consisting of copper + 1 atoms / hfac alone and stored for 3 months. A copper thin film was formed. The film thickness, specific resistance, and surface roughness were also measured in the same manner as in the examples. Table 13 shows the results. <Comparative Example 2> MOCVD was performed under the same conditions as in Example 1 except that the substrate temperature was set to 180 ° C. using a copper thin film forming solution raw material consisting of copper + 1 tmvs · hfac alone and stored for 3 months.
A copper thin film was formed by the method. The film thickness, specific resistance, and surface roughness were also measured in the same manner as in the examples. Table 13 shows these results.
Shown in
【００６９】[0069]
【表１３】 [Table 13]
【００７０】表１３から明らかなように、比較例１及び
比較例２では１分間で成長した膜厚がそれぞれ３０ｎｍ
及び２０ｎｍと上述した実施例１〜１１と比較して極め
て小さかった。膜の比抵抗値は２．２μΩｃｍ及び２．
４μΩｃｍであり、理論値１．６μΩｃｍと大きくかけ
離れていた。表面粗さは平均１．５ｎｍ及び２．５ｎｍ
であり、上述した実施例１〜１１と比較して極めて劣っ
ていた。As apparent from Table 13, in Comparative Examples 1 and 2, the film thickness grown in one minute was 30 nm.
And 20 nm, which were extremely small as compared with Examples 1 to 11 described above. The specific resistance of the film is 2.2 μΩcm and 2.
4 μΩcm, which was far from the theoretical value of 1.6 μΩcm. Surface roughness average 1.5nm and 2.5nm
This was extremely inferior to Examples 1 to 11 described above.
【００７１】[0071]
【発明の効果】以上述べたように、請求項１に係る銅+1
(アリルアルコキシシラン)(ヘキサフルオロアセチルア
セトン)からなる有機金属化学蒸着用有機銅化合物は、
単独で銅薄膜形成用溶液原料とすることにより、下地膜
との密着性が高まるとともに成膜速度がより一層向上
し、成膜前の有機銅化合物はその分解が抑制され、長い
寿命を有する。また請求項３，６又は９に係る発明によ
れば、上記有機銅化合物を銅+1ａｔｍｓ・ｈｆａｃ、銅
+1ｔｍｖｓ・ｈｆａｃ、又は銅+1ｔｍｏｖｓ・ｈｆａｃ
のようなベースとなる別の一価の銅金属を含む有機銅化
合物の溶剤として用いることにより、成膜初期に銅+1ａ
ｔｍｓ・ｈｆａｃ、銅+1ｔｍｖｓ・ｈｆａｃ又は銅+1ｔ
ｍｏｖｓ・ｈｆａｃが分解し易く、これにより下地膜で
の初期の銅成長が起り易くなり、銅薄膜の成長速度が増
大する。As described above, the copper +1 according to claim 1 is used.
(Allylalkoxysilane) (hexafluoroacetylacetone) organometallic chemical vapor deposition organic copper compound consisting of
By using the solution raw material alone for forming a copper thin film, the adhesion to the underlying film is enhanced and the film formation rate is further improved, and the decomposition of the organic copper compound before film formation is suppressed, and the organic copper compound has a long life. According to the third, sixth or ninth aspect of the present invention, the organic copper compound is made of copper +1 atms · hfac, copper
+1 tmvs · hfac or copper +1 tmvs · hfac
By using as a solvent of another organic copper compound containing monovalent copper metal as a base, copper +1 a
tms · hfac, copper +1 tmvs · hfac or copper +1 t
movs · hfac is easily decomposed, whereby initial copper growth on the underlayer is likely to occur, and the growth rate of the copper thin film is increased.
【００７２】また請求項５，８，１１又は１３に係る発
明によれば、ベースとなる有機銅化合物に更にａｔｍ
ｓ、ｔｍｖｓ、ｔｍｏｖｓ、ａｔｍｏｓのうち少なくと
も１種を加えることにより、ａｔｍｓ等における炭素二
重結合が溶液中に増加し、Ｃｕのπ結合が高まり、成膜
前の保存状態で有機銅化合物の分解が抑制され、長い寿
命の溶液となる。更に本発明の有機銅化合物の溶液原料
を用いてＭＯＣＶＤ法により成膜した銅薄膜は、従来の
ものと比べてバルク銅と同程度の理論値に近い抵抗値を
有する高純度を示し、下地膜と堅牢に密着しかつ表面粗
さが小さい特長を有する。この銅薄膜は銅多層配線用の
深いコンタクトホールの埋込みにおいても極めて有効で
ある。According to the fifth, eighth, eleventh and thirteenth aspects of the present invention, the organic copper compound serving as a base is further provided with atm
By adding at least one of s, tmvs, tmovs, and atmos, the carbon double bond in atms and the like increases in the solution, the π bond of Cu increases, and the organic copper compound is decomposed in a storage state before film formation. Is suppressed and a long-life solution is obtained. Further, the copper thin film formed by MOCVD using the solution raw material of the organic copper compound of the present invention shows high purity having a resistance value close to the theoretical value of the same level as that of bulk copper compared to the conventional one, It has the feature that it is firmly adhered to and has low surface roughness. This copper thin film is extremely effective in filling deep contact holes for copper multilayer wiring.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｃ０７Ｆ 7/08 Ｃ０７Ｆ 7/08 Ｃ 19/00 19/00 Ｆターム(参考） 4H048 AA01 AB78 VA56 VB10 4H049 VN01 VP01 VQ03 VQ95 VR21 VR43 VU24 4H050 AB78 4K030 BA01 CA01 LA11 4M104 BB04 DD45 HH09 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification code FI theme coat ゛ (reference) C07F 7/08 C07F 7/08 C 19/00 19/00 F term (reference) 4H048 AA01 AB78 VA56 VB10 4H049 VN01 VP01 VQ03 VQ95 VR21 VR43 VU24 4H050 AB78 4K030 BA01 CA01 LA11 4M104 BB04 DD45 HH09
Claims (14)
ルコキシシラン)(ヘキサフルオロアセチルアセトン)で
あって、 Ｒ1、Ｒ2及びＲ3がメチル基、エチル基、プロピル基及
びブチル基からなる群より選ばれたアルキル基であるこ
とを特徴とする有機金属化学蒸着用有機銅化合物。 【化１】 1. A copper +1 (allylalkoxysilane) (hexafluoroacetylacetone) represented by the following formula (1), wherein R 1 , R 2 and R 3 are methyl, ethyl, propyl and butyl. An organocopper compound for metalorganic chemical vapor deposition, which is an alkyl group selected from the group consisting of groups. Embedded image
銅化合物からなる銅薄膜形成用溶液原料。2. A solution raw material for forming a copper thin film, comprising the organocopper compound for metalorganic chemical vapor deposition according to claim 1.
リメチルシラン)(ヘキサフルオロアセチルアセトン)に
請求項１記載の有機金属化学蒸着用有機銅化合物を添加
して前記銅+1(アリルトリメチルシラン)(ヘキサフルオ
ロアセチルアセトン)を溶解してなる銅薄膜形成用溶液
原料。 【化２】 Wherein the added the following copper represented by the formula (2) +1 (allyltrimethylsilane) metal organic chemical vapor deposition for organic copper compound of claim 1 wherein in (hexafluoroacetylacetone) copper +1 ( A solution raw material for forming a copper thin film obtained by dissolving allyltrimethylsilane) (hexafluoroacetylacetone). Embedded image
銅化合物の添加量が１〜２０重量％である請求項３記載
の銅薄膜形成用溶液原料。4. The solution raw material for forming a copper thin film according to claim 3, wherein the amount of the organic copper compound for metal organic chemical vapor deposition according to claim 1 is 1 to 20% by weight.
フルオロアセチルアセトン)に請求項１記載の有機金属
化学蒸着用有機銅化合物０．０１〜２０重量％とアリル
トリメチルシラン、トリメチルビニルシラン、トリメト
キシビニルシラン及びアリルトリメトキシシランからな
る群より選ばれた１種又は２種以上の化合物０．０１〜
４０重量％とを添加して前記銅+1(アリルトリメチルシ
ラン)(ヘキサフルオロアセチルアセトン)を溶解してな
る銅薄膜形成用溶液原料。5. An organic copper compound for metalorganic chemical vapor deposition according to claim 1, comprising 0.01 to 20% by weight of copper + 1 (allyltrimethylsilane) (hexafluoroacetylacetone) and allyltrimethylsilane, trimethylvinylsilane, trimethoxyvinylsilane. And one or more compounds selected from the group consisting of
A solution raw material for forming a copper thin film obtained by dissolving the above-mentioned copper + 1 (allyltrimethylsilane) (hexafluoroacetylacetone) with the addition of 40% by weight.
ルビニルシラン)(ヘキサフルオロアセチルアセトン)に
請求項１記載の有機金属化学蒸着用有機銅化合物を添加
して前記銅+1(トリメチルシラン)(ヘキサフルオロアセ
チルアセトン)を溶解してなる銅薄膜形成用溶液原料。 【化３】 6. Copper +1 (trimethylvinylsilane) represented by the following formula (3) (hexafluoro acetylacetone) in claim 1 organometallic chemical vapor deposition for organic copper compound is added the copper + 1 (trimethyl according A solution material for forming a copper thin film obtained by dissolving silane) (hexafluoroacetylacetone). Embedded image
銅化合物の添加量が１〜２０重量％である請求項６記載
の銅薄膜形成用溶液原料。7. The solution raw material for forming a copper thin film according to claim 6, wherein the amount of the organic copper compound for metalorganic chemical vapor deposition according to claim 1 is 1 to 20% by weight.
フルオロアセチルアセトン)に請求項１記載の有機金属
化学蒸着用有機銅化合物０．０１〜２０重量％とアリル
トリメチルシラン、トリメチルビニルシラン、トリメト
キシビニルシラン及びアリルトリメトキシシランからな
る群より選ばれた１種又は２種以上の化合物０．０１〜
４０重量％とを添加して前記銅+1(トリメチルビニルシ
ラン)(ヘキサフルオロアセチルアセトン)を溶解してな
る銅薄膜形成用溶液原料。8. An organic copper compound for metalorganic chemical vapor deposition according to claim 1, comprising 0.01 to 20% by weight of copper + 1 (trimethylvinylsilane) (hexafluoroacetylacetone) and allyltrimethylsilane, trimethylvinylsilane, trimethoxyvinylsilane and One or more compounds selected from the group consisting of allyltrimethoxysilane
A solution raw material for forming a copper thin film obtained by dissolving the above-mentioned copper +1 (trimethylvinylsilane) (hexafluoroacetylacetone) with the addition of 40% by weight.
キシビニルシラン)(ヘキサフルオロアセチルアセトン)
に請求項１記載の有機金属化学蒸着用有機銅化合物を添
加して前記銅+1(トリメトキシビニルシラン)(ヘキサフ
ルオロアセチルアセトン)を溶解してなる銅薄膜形成用
溶液原料。 【化４】 9. Copper + 1 (trimethoxyvinylsilane) represented by the following formula (4) (hexafluoroacetylacetone)
A copper thin film forming solution raw material obtained by adding the organocopper compound for organometallic chemical vapor deposition according to claim 1 to dissolve the copper + 1 (trimethoxyvinylsilane) (hexafluoroacetylacetone). Embedded image
機銅化合物の添加量が１〜２０重量％である請求項９記
載の銅薄膜形成用溶液原料。10. The solution raw material for forming a copper thin film according to claim 9, wherein the amount of the organic copper compound for metal organic chemical vapor deposition according to claim 1 is 1 to 20% by weight.
キサフルオロアセチルアセトン)に請求項１記載の有機
金属化学蒸着用有機銅化合物０．０１〜２０重量％とア
リルトリメチルシラン、トリメチルビニルシラン、トリ
メトキシビニルシラン及びアリルトリメトキシシランか
らなる群より選ばれた１種又は２種以上の化合物０．０
１〜４０重量％とを添加して前記銅+1(トリメトキシビ
ニルシラン)(ヘキサフルオロアセチルアセトン)を溶解
してなる銅薄膜形成用溶液原料。11. An organic copper compound for metalorganic chemical vapor deposition according to claim 1 in an amount of 0.01 to 20% by weight of copper + 1 (trimethoxyvinylsilane) (hexafluoroacetylacetone) and allyltrimethylsilane, trimethylvinylsilane, trimethoxyvinylsilane. And one or more compounds selected from the group consisting of
A solution raw material for forming a copper thin film obtained by adding 1 to 40% by weight and dissolving the copper + 1 (trimethoxyvinylsilane) (hexafluoroacetylacetone).
サフルオロアセチルアセトン)に銅+1(トリメトキシビニ
ルシラン)(ヘキサフルオロアセチルアセトン)又は銅
+1(トリメチルビニルシラン)(ヘキサフルオロアセチル
アセトン)０．０１〜２０重量％を添加して前記銅+1(ア
リルトリメチルシラン)(ヘキサフルオロアセチルアセト
ン)を溶解してなる銅薄膜形成用溶液原料。12. Copper + 1 (trimethoxyvinylsilane) (hexafluoroacetylacetone) or copper + 1 (allyltrimethylsilane) (hexafluoroacetylacetone)
A solution raw material for forming a copper thin film obtained by adding 0.01 to 20% by weight of +1 (trimethylvinylsilane) (hexafluoroacetylacetone) to dissolve the copper +1 (allyltrimethylsilane) (hexafluoroacetylacetone).
サフルオロアセチルアセトン)に銅+1(トリメトキシビニ
ルシラン)(ヘキサフルオロアセチルアセトン)又は銅
+1(トリメチルビニルシラン)(ヘキサフルオロアセチル
アセトン)０．０１〜２０重量％とアリルトリメチルシ
ラン、トリメチルビニルシラン、トリメトキシビニルシ
ラン及びアリルトリメトキシシランからなる群より選ば
れた１種又は２種以上の化合物０．０１〜４０重量％と
を添加して前記銅+1(アリルトリメチルシラン)(ヘキサ
フルオロアセチルアセトン)を溶解してなる銅薄膜形成
用溶液原料。13. Copper +1 (allyltrimethylsilane) copper (hexafluoroacetylacetone) +1 (trimethoxyvinylsilane) (hexafluoroacetylacetone) or copper
+1 (trimethylvinylsilane) (hexafluoroacetylacetone) 0.01 to 20% by weight and one or more compounds 0 selected from the group consisting of allyltrimethylsilane, trimethylvinylsilane, trimethoxyvinylsilane and allyltrimethoxysilane 0.1 to 40% by weight to dissolve the copper + 1 (allyltrimethylsilane) (hexafluoroacetylacetone).
薄膜形成用溶液原料により形成された銅薄膜。14. A copper thin film formed from the solution raw material for forming a copper thin film according to claim 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28806699A JP4102954B2 (en) | 1999-10-08 | 1999-10-08 | Organocopper compound for metalorganic chemical vapor deposition, solution raw material for forming copper thin film containing the same, and copper thin film made therefrom |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28806699A JP4102954B2 (en) | 1999-10-08 | 1999-10-08 | Organocopper compound for metalorganic chemical vapor deposition, solution raw material for forming copper thin film containing the same, and copper thin film made therefrom |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2001114789A true JP2001114789A (en) | 2001-04-24 |
| JP4102954B2 JP4102954B2 (en) | 2008-06-18 |
Family
ID=17725389
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28806699A Expired - Fee Related JP4102954B2 (en) | 1999-10-08 | 1999-10-08 | Organocopper compound for metalorganic chemical vapor deposition, solution raw material for forming copper thin film containing the same, and copper thin film made therefrom |
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| Country | Link |
|---|---|
| JP (1) | JP4102954B2 (en) |
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- 1999-10-08 JP JP28806699A patent/JP4102954B2/en not_active Expired - Fee Related
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| Publication number | Publication date |
|---|---|
| JP4102954B2 (en) | 2008-06-18 |
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