JP2002193988A - Stabilized copper complex and method of producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a copper complex for MOCVD that is easily vaporizable with high vapor pressure, easily controllable in formation rate of copper film and stable at high temperature. SOLUTION: Stabilized copper complex having general formula 1 produced by reacting β-ketimine ligand and a copper (I) compound in the presence of an electron donating compound of general formula (1) (R1 or R2 is a 1-20C fluorohydrocarbon group or 1-20C hydrocarbon group, and at least either R1 or R2 is the fluorohydrocarbon group. R3 is H, F or a 1-20C fluorohydrocarbon group. R4 is a 1-20C fluorohydrocarbon group, 1-20C hydrocarbon group or H. L is an electron donating compound such as an unsaturated hydrocarbon which may contain a hetero atom, either, silyl ether, phosphine or amine).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a copper complex suitable for forming a copper thin film layer. In particular, the present invention relates to a copper complex suitable for use in forming a high-speed high-integration 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]

2. Description of the Related Art In manufacturing technology in the field of integrated circuits in the electronics industry, demands for high integration and high speed are increasing. At present, aluminum wiring is used for most integrated circuits. However, with the demand for higher integration and higher speed, a wiring technique using copper having lower electric resistance and migration resistance is being put to practical use.

[0003] Regarding the technique of forming copper wiring, zero-valent Cu
A method combining a sputtering method (hereinafter referred to as copper (0)) and a solution plating method of divalent Cu (hereinafter referred to as copper (II)) and mainly a monovalent Cu (hereinafter referred to as copper (I)) Chemical vapor deposition (hereinafter referred to as MO) using an organometallic complex
CVD method). However, in the former method combining the sputtering method and the plating method, 0.15 μm
It has been found that it is difficult to fill a deep groove having a small diameter of about m or less. In order to solve this problem, the MOCVD method has been used, and it has become possible to coat grooves, holes and steps having a high depth / diameter ratio (high aspect ratio) with small unevenness and smooth and excellent film quality.

[0004] Copper compounds include copper (II) bis (acetylsetnato) and copper (II) bis (trimethylacetylacetonate), which are solid and have a low vapor pressure and are unsuitable as copper MOCVD materials. is there.

On the other hand, copper (II) having a structure similar to these copper compounds and having a fluorine atom in its ligand
Bis (hexafluoroacetylacetonate) copper has been used for a long time because it has a high vapor pressure despite being solid. This is because the intermolecular interaction is reduced by the fluorination. Copper (II) bis (hexafluoroacetylacetonate) copper and its hydrates have been described by Van Herert et al. Elec
trochem. Soc. , 112, 1123 (196
It has been reported that 5) is used as a Cu-MOCVD material. At this time, the copper compound was heated to 150 ° C., and hydrogen gas at 90 ° C. was used as a carrier gas.
Is deposited while reducing copper (II) to copper (0). At this time, the hexafluoroacetylacetonate anion, which is a ligand, is hydrogenated to hexafluoroacetylacetone, and is discharged out of the system.

[0006] Cu-MOCVD of copper (II) compounds using Schiff base ligand, ie β-ketoimine ligand
Materials have also been proposed. For example, USP 3,594,
No. 216 discloses that bis (acetylacetoneethylenediimino) copper (II) and bis (acetylacetoneimino)
Copper (II) has been proposed, evaporating above 200 ° C. and depositing above 400 ° C. on a substrate. Also, Ma
ter. Res. Soc. Symp. Proc. 20
No. 4,415 (1990) proposes a copper (II) compound having a fluorinated type Schiff base ligand.
It is evaporated at a temperature of about 00 ° C. and deposited on a substrate at a temperature of about 300 ° C.

[0007] In the above proposal, the deposition temperature is 200
Cu-MOCVD which can be deposited at a lower temperature than ℃
Material was desired.

[0008] The organic metal compound of copper (I) has realized the deposition temperature of 200 ° C or less. Specifically, it is a cyclopentadienyl copper (I) trialkylphosphine complex, which is described in Chem. Mater. 2,636 (199
In (0), 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 and selectivity to metals and insulators. Furthermore, cyclopentadienyl copper (I) trialkyl phosphine itself has a problem of stability even when used for a long time at a relatively low temperature of around 70 ° C. with precipitation of copper (0). .

Further, it is a solid like copper (II) described above, and has a problem that the evaporation rate and the evaporation rate depend on the shape, particle size and particle size distribution of the solid particles.

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. 2132693. 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 a conventional solid compound. However, hexafluoroacetylacetonate copper (I) vinyltrimethylsilane is gradually decomposed by prolonged heating for vaporization, copper (0) is deposited, and a vinylsilane compound is contained in the structure. In addition, when the vaporization operation is performed at a high temperature for a long time, oligomers and polymers thereof are generated, which may cause blockage in the apparatus.

[0011]

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and has as its object to solve the problems of the prior art. That is, the present invention has a high vapor pressure and facilitates vaporization. It is an object of the present invention to provide a copper complex for MOCVD which can easily control the formation rate of a copper thin film and is stable at a high temperature.

[0012]

Means for Solving the Problems The present inventors have found that a β-ketoimine ligand and a copper compound having an electron donating compound are thermally stable and have a high vapor pressure. As a result, they have found a copper compound capable of forming a high-quality copper thin film at a controllable rate, and have completed the present invention.

That is, the present invention provides the following general formula (1)

[0014]

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(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,
At least one of R ¹ and R ² is a fluorinated hydrocarbon group. R
³ is a hydrogen atom, a fluorinated hydrocarbon radical of fluorine atom or a C 1-20, R ⁴ is fluorinated hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group or a hydrogen atom having 1 to 20 carbon atoms Express. L represents an electron-donating compound such as an unsaturated hydrocarbon, ether, silyl ether, phosphine or amine which may contain a hetero atom. ), A copper complex composition using the stabilized copper complex, and methods for producing the same.

Hereinafter, the present invention will be described in detail.

In the above general formula (1), R ¹ and R ² are:
It is 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. If the number of carbon atoms exceeds 20, it is not preferable because it is difficult to procure raw materials and to purchase high-purity raw materials.

The fluorinated hydrocarbon group is not particularly limited as long as it is a hydrocarbon group having at least one fluorine atom and having 1 to 20 carbon atoms, and is a fluorinated saturated hydrocarbon group or a non-fluorinated hydrocarbon group. And a saturated hydrocarbon group.

Examples of the fluorinated saturated hydrocarbon group include trifluoromethyl, perfluoroethyl, perfluoropropyl, perfluorocyclopropyl, perfluoromethylcyclopropyl, perfluorobutyl, and perfluorocyclo. Perfluorocarbon residues such as butyl group, perfluoropentyl group, perfluorocyclopentyl group, perfluoromethylcyclopentyl group, perfluorohexyl group, perfluorocyclohexyl group, perfluoro-1,2-dimethylcyclohexyl group and perfluoroheptyl group , Fluoromethyl group, difluoromethyl group, 1,1,1-trifluoroethyl group, 2
And a fluorohydrocarbon residue of a perfluoroalkylethyl group.

Examples of the fluorinated unsaturated hydrocarbon group include, for example, perfluoroethenyl, perfluoropropenyl, perfluoro-1,3-butadienyl, cyclobutenyl, perfluoro-2-butynyl, pentafluoro Examples include a phenyl group, a perfluorotoluyl group, a bis (trifluoromethyl) phenyl group, a perfluoronaphthalenyl group, a perfluoroindenyl group, and a perfluorofluorenyl group.

The hydrocarbon group is a hydrocarbon group having 1 to 20 carbon atoms, and preferably includes an alkyl group, an aryl group, an arylalkyl group and an alkylaryl group having 1 to 10 carbon atoms. Specifically, for example, a methyl group, an ethyl group, an n-propyl group, an i-propyl group,
n-butyl group, i-butyl group, sec-butyl group, te
rt. -Butyl group, n-pentyl group, tert. -Amyl, n-hexyl, cyclohexyl, phenyl, toluyl and the like.

R ¹ and R ² may be the same or different.

R ³ is a hydrogen atom, a fluorine atom or R ¹ , R ²
And the same fluorocarbon groups having 1 to 20 carbon atoms. If the number of carbon atoms exceeds 20, it is not preferable because it is difficult to procure raw materials and to purchase high-purity raw materials.

R ⁴ has the same carbon number as 1 to 20 as R ¹ and R ^2.
Represents a fluorinated hydrocarbon group, a hydrocarbon group having 1 to 20 carbon atoms, or a hydrogen atom. If the number of carbon atoms exceeds 20, it is not preferable because it is difficult to procure raw materials and to purchase high-purity raw materials.

L is selected from the group of electron-donating compounds such as unsaturated hydrocarbons, ethers, silyl ethers, phosphines or amines which may contain heteroatoms.

The unsaturated hydrocarbon which may contain a hetero atom includes, for example, alkene, alkene containing a hetero atom, alkyne and alkyne containing a hetero atom.
Alkenes include linear olefins and branched olefins, and heteroatom-containing alkenes include vinylsilane compounds. As the alkyne or the hetero atom-containing alkene, a compound having a structure having no hydrogen atom directly connected to a triple bond is preferable, and a compound having a hetero atom-containing substituent such as a hydrocarbon group or silicon bonded to both ends of the triple bond may be mentioned. it can. A specific example thereof will be described later.

As the ether, monoethers and polyethers containing at least one oxygen atom in the molecule can be used, and those having a linear, branched or cyclic structure can be used. For example, as monoethers, diethyl ether, diisopropyl ether, dibutyl ether, tert. -Butyl methyl ether, tetrahydrofuran, dihydropyran, tetrahydropyran and the like, and as the polyethers,
1,2-dimethoxyethane, 1,3-dimethoxypropane, 2,2-di-tert. -Butyl-1,3-dimethoxypropane, 2,2-di-i-butyl-1,3-dimethoxypropane, 2,2-diphenyl-1,3-dimethoxypropane and the like.

As the silyl ether, the following general formula (4)

[0029]

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(R ¹³ and R ^{14 each} represent a hydrocarbon group having 1 to 50 carbon atoms, preferably a hydrocarbon group having 1 to 20 carbon atoms, and n represents an integer of 1 to 3). The indicated silyl ethers can be used. For example, trimethylmethoxysilane, dimethyldimethoxysilane, methyltrimethoxysilane, triethylmethoxysilane, diethyldimethoxysilane, ethyltrimethoxysilane, n
-Propyltrimethoxysilane, di-n-propyldimethoxysilane, tri-n-propylmethoxysilane, i
-Propyltrimethoxysilane, di-i-propyldimethoxysilane, tri-i-propylmethoxysilane, n
-Butyltrimethoxysilane, i-butyltrimethoxysilane, sec. -Butyltrimethoxysilane, ter
t. -Butyltrimethoxysilane, di-i-butyldimethoxysilane, di-tert. -Butyldimethoxysilane, tert. -Butylmethyldimethoxysilane, te
rt. -Butylethyldimethoxysilane, tert. −
Butyl-n-propyldimethoxysilane, diphenyldimethoxysilane, tert. -Butyl-tert. -Butoxydimethoxysilane and the like.

As the phosphine, the following general formula (5)

[0032]

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(R ¹⁵ is a hydrocarbon group having 1 to 50 carbon atoms, and preferably represents a hydrocarbon group having 1 to 20 carbon atoms). For example, trimethylphosphine, triethylphosphine,
Tri-n-propylphosphine, tri-i-propylphosphine, tri-n-butylphosphine, tri-i-butylphosphine, tri-sec. -Butylphosphine,
Tri-tert. -Butylphosphine, triphenylphosphine, tritolylphosphine.

As the amine, polyamines such as monoamine and polyalkylene polyamine can be used.

For example, as monoamines, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, n-propylamine, di-n-propylamine, tri-n-propylamine, i-propylamine, di-i -Propylamine, tri-i-propylamine, n-butylamine, di-n-butylamine, tri-n-butylamine, i-butylamine, sec. -Butylamine, tert. -Butylamine, tri-n-octylamine, 2-ethylhexylamine, di-2-ethylhexylamine, allylamine, diallylamine, triallylamine, and the like.Examples of polyamines include ethylenediamine, tetramethylethylenediamine, diethylenetriamine, and triethylene. Examples thereof include polyalkylene polyamines such as tetramine, tetraethylenepentamine, piperazine, N-methylpiperazine, and N-aminoethylpiperazine.

These electron donating compounds may be used alone or as a mixture of a plurality.

Among them, a copper complex in which the electron donating compound L is an alkene, alkyne, alkene containing a hetero atom, or alkyne containing a hetero atom is preferable. Above all, the following general formula (2)

[0038]

Embedded image

(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,
At least one of R ¹ and R ² is a fluorinated hydrocarbon group. R
³ is a hydrogen atom, a fluorinated hydrocarbon radical of fluorine atom or a C 1-20, R ⁴ is fluorinated hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group or a hydrogen atom having 1 to 20 carbon atoms Express. R ⁵ , R ⁶ , R ⁷ , and R ^{8 each} represent a hydrogen atom and have 1 to 20 carbon atoms.
Represents a hydrocarbon group or a hetero atom-containing substituent. )
Is preferably an alkene.

R ¹ , R ² , R ³ and R ⁴ are represented by the above general formula (1)
The specific example is similar to the above example. Taking into account the procurement of raw materials and purity, the number of carbon atoms is preferably 20 or less.

Specific examples of alkenes include, for example, butene-1, pentene-1, hexene-1, octene-1,
Linear olefins such as decene-1 and dodecene-1, branched olefins such as isobutene, 3-methyl-butene-1, and 4-methylpentene-1; cyclic alkyl-substituted olefins such as vinylcyclohexane; cyclohexene; Cyclic olefins such as dienes, styrene, p-methylstyrene, p-tert. -Butoxystyrene, p
-Aromatic substituted vinyl compounds such as trimethylsilylstyrene, and vinylsilanes such as vinyltrimethylsilane, vinyltrimethoxysilane, divinyldimethylsilane, and allyltrimethylsilane.

Above all, the following general formula (3)

[0043]

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(Wherein R ⁹ is a hydrogen atom, having 1 to 20 carbon atoms)
Or a fluorinated hydrocarbon group having 1 to 20 carbon atoms, wherein R ¹⁰ , R ¹¹ and R ¹² represent a hydrocarbon group having 1 to 20 carbon atoms, and n represents an integer of 0 to 20. ) Is more preferably a copper complex in which the electron donating compound L is a silicon-containing alkene.

R ⁹ is the same fluorinated hydrocarbon group, hydrocarbon group or hydrogen atom as R ¹ and R ^{2 in} the general formula (1), and specific examples thereof are the same as those described above. Taking into account the procurement of raw materials and purity, the number of carbon atoms is preferably 20 or less.

Examples of the alkene include vinyltrimethylsilane, allyltrimethylsilane, butenyltrimethylsilane, pentenyltrimethylsilane, hexenyltrimethylsilane, heptenyltrimethylsilane, octenyltrimethylsilane, decenyltrimethylsilane, vinyl tert. -Butyldimethylsilane, allyl ter
t. -Butyldimethylsilane, butenyl tert. -Butyldimethylsilane, pentenyl tert. -Butyldimethylsilane, hexenyl tert. -Butyldimethylsilane, heptenyl tert. -Butyldimethylsilane, octenyl tert. -Butyldimethylsilane, decenyl tert. -Butyldimethylsilane, vinyl di-t
ert. -Butylmethylsilane, allyl ditert. −
Butylmethylsilane, butenyl ditert. -Butylmethylsilane, pentenylditert. -Butylmethylsilane, hexenylditert. -Butylmethylsilane,
Heptenyl ditert. -Butyldimethylsilane, octenylditert. -Butylmethylsilane, decenylditert. -Butylmethylsilane, vinyldimethylmethoxysilane, allyldimethylmethoxysilane, vinylmethyldimethoxysilane, allylmethyldimethoxysilane, vinyltrimethoxysilane, allyltrimethoxysilane, vinyl tert. -Butyldimethoxysilane, allyl tert. -Butyl dimethoxysilane, vinyl di-t
ert. -Butylmethoxysilane, allyl ditert.
-Butylmethoxysilane.

The method for synthesizing the stabilized copper complex represented by the above general formula (1) in the present invention comprises reacting a fluorinated β-diketone with ammonia or an amine to form β-ketoimine, and then converting the electron donating compound. It can be synthesized by reacting a copper (I) compound in the coexistence. A proton on the carbon between the ketone and the imine of β-ketimine is extracted with an alkali metal or the like in the absence of an electron donating compound, and the copper (I) compound is reacted to synthesize a β-ketoimine copper complex. It is also possible to adopt a method of adding an active compound to coordinate.

The solvent used for synthesizing the stabilized copper complex is not particularly limited as long as it is used in the art. For example, saturated hydrocarbons such as n-pentane, i-pentane, n-hexane, n-heptane, n-decane, unsaturated hydrocarbons such as toluene, xylene and decene-1, diethyl ether, tetrahydrofuran, tetrahydropyran And halogenated hydrocarbons such as dichloromethane, dichloroethane, chloroform, and chlorobenzene.

The reaction temperature at the time of synthesizing the stabilized copper complex is not particularly limited, but it is preferable to perform the reaction in a temperature range that does not decompose the formed copper compound. Usually, in the range of −78 to 200 ° C., which is a temperature used industrially,
Preferably, it is performed in the range of -50 to 150 ° C. The pressure condition of the reaction may be any of pressurization, normal pressure and reduced pressure.

The method of purifying the synthesized stabilized copper complex is not particularly limited, but distillation under reduced pressure and column separation and purification using silica, alumina or a polymer gel can be used. The operation at this time follows the method in the field of organometallic compound synthesis. That is, it is preferable that the dehydration and deoxygenation be performed in a nitrogen or argon atmosphere, and the solvent to be used and the column filler for purification be subjected to a dehydration operation in advance. This operation may improve the yield and purity of the produced copper compound.

The stabilized copper complex thus purified is
It can be used as it is for forming a copper thin film on a substrate by a chemical vapor deposition method. For 1 mol of stabilized copper complex,
The above electron donating compound L is further added to 0.01 mol to 10 mol
By using the composition to which mol has been added, even when a chemical vapor deposition operation is performed for a long time, problems such as blockage in the apparatus do not occur or are alleviated.

The temperature during the chemical vapor deposition operation in the present invention is not particularly limited, but is usually in the range of 0 ° C. to 200 ° C. Further, any carrier used in the technical field as a carrier gas can be used. For example, hydrogen, nitrogen,
Argon etc. are mentioned.

[0053]

EXAMPLES Examples are shown below, but the present invention is not limited to these examples.

Example 1 In a nitrogen stream, a Journa was placed in a 200 ml Schlenk tube.
l of Fluorine Chemistry, 2
7 (1985) 371-378, synthesized from hexafluoroacetylacetone and ammonia.
1,1,5,5,5-hexafluoro-2-aminopentan-4-4one 20.70 g (0.100 mol)
Is diluted with 100 ml of dehydrated tetrahydrofuran,
After adding 4.01 g (0.100 mol) of potassium hydride, the mixture was stirred at room temperature to obtain a potassium salt solution.

The obtained potassium salt solution was treated with copper (I) chloride.
A mixture of 9.90 g (0.100 mol), 10.01 g (0.100 mol) of vinyltrimethylsilane, and 100 ml of tetrahydrofuran was dropped at room temperature.
Stirred at 0 ° C. for 4 hours. After the residue was filtered off with a glass filter, tetrahydrofuran was distilled off and distilled under reduced pressure.
25.13 g of (1,1,1,5,5,5-hexafluoro-2-aminopentane-4-onato) copper (I) vinyltrimethylsilane as the target substance (0.0680 mol)
1) was obtained. The yield corresponded to 68%. The results of the elemental analysis are as follows.

C ₁₀ H ₁₄ NOF ₆ SiCu wt% Actual values (C32.2, H3.7, N3.8, F30.
9, Cu 17.1, Si 7.4) Theoretical values (C32.5, H3.8, N3.8, F30.
8, Cu 17.2, Si 7.6) Example 2 In Example 1, vinyltrimethylsilane 10.0
(1,1,1,5,) in the same manner as in Example 1 except that 11.1 g (0.100 mol) of allyltrimethylsilane was used instead of 1 g (0.100 mol).
5,5-Hexafluoro-2-aminopentane-4-onato) copper (I) allyltrimethylsilane was synthesized. The result was a yield of 72%, and the result of elemental analysis was as follows.

C ₁₀ H ₁₄ NOF ₆ SiCu wt% Measured value (C34.5, H4.2, N4.0, F29.
9, Cu 16.8, Si 7.1) Theoretical values (C34.4, H4.2, N4.2, F29.
7, Cu 16.6, Si 7.3)

[0058]

As described above, according to the present invention, it is possible to obtain a novel copper complex having high thermal stability and a vapor pressure at room temperature, and particularly to obtain a copper complex suitable as a MOCVD material for copper wiring. it is obvious.

Further, in synthesizing a copper (I) complex having β-ketoimine as a ligand, an extremely efficient and economical synthesis recipe can be provided.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (Reference) H01L 21/285 301 H01L 21/285 301Z

Claims (7)

[Claims] (1) The following general formula (1): (Wherein, R ¹ and R ² are a fluorocarbon 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 fluorohydrocarbon group. R ³ represents a hydrogen atom, a fluorine atom or a fluorinated hydrocarbon group having 1 to 20 carbon atoms, and R ⁴ represents a fluorinated hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms or L represents a hydrogen atom, and L represents an electron-donating compound such as an unsaturated hydrocarbon, ether, silyl ether, phosphine or amine which may contain a hetero atom.) 2. The stabilized copper complex according to claim 1, wherein L is alkene, alkyne, alkene containing a hetero atom, or alkyne containing a hetero atom. 3. The following general formula (2): (Wherein, R ¹ and R ² are a fluorocarbon 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 fluorohydrocarbon group. R ³ represents a hydrogen atom, a fluorine atom or a fluorinated hydrocarbon group having 1 to 20 carbon atoms, and R ⁴ represents a fluorinated hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms or Represents a hydrogen atom, R ⁵ ,
R ⁶ , R ⁷ and R ^{8 each} represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a heteroatom-containing substituent having 1 to 20 carbon atoms. 3. The stabilized copper complex according to claim 2, wherein 4. A compound represented by the following general formula (3): (Wherein, R ⁹ is a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a fluorinated hydrocarbon group having 1 to 20 carbon atoms, and R ¹⁰ and R ^10
11 and R ¹² represent a hydrocarbon group having 1 to 20 carbon atoms, and n represents an integer of 0 to 20). 5. The stabilized copper complex according to any one of claims 1 to 4, wherein the amount of the copper complex is 0.01 mol to 1 mol.
A copper complex composition to which 0 mol of an electron donating compound is added. 6. A copper thin film is formed on a substrate by chemical vapor deposition using the stabilized copper complex according to any one of claims 1 to 4 or the copper complex composition according to claim 5. How to form. 7. A method according to claim 1, wherein ammonia or an amine is reacted with the fluorinated β-diketone to form β-ketoimine, and then a monovalent copper compound is reacted in the presence of an electron donating compound. 5. The method for producing a stabilized copper complex according to any one of 4.