JP2001328953A - Copper(i) beta-diketonate complex having allene compound as ligand and its production method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a copper(I) beta-diketonate complex for forming a copper thin film through metal organics chemical vapor deposition(MOCVD) and its production method. SOLUTION: The copper(I) beta-diketonate complex represented by general formula (2) (R6 and R7 are each same or different and a linear or branched 1-4C alkyl, a 1-4C alkoxy or a linear or branched fluorine-substituted 1-4C alkyl; R8 is a hydrogen atom or a fluorine atom) having an allene compound represented by general formula (1) [R1-R4 are each same or different and a hydrogen atom, a 1-4C alkyl or (R5)3Si; R1 and R2 may form a 3-6 membered ring; R2 and R3 may form a 8-10 membered ring; R5 is one or more kinds of a linear or branched 1-4C alkyl] and its production method are disclosed. Formula (3) (L is 1,2-cyclononadiene) is exemplified.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a .beta.-diketonate copper (I) complex useful for forming a copper thin film by metalorganic chemical vapor deposition (hereinafter abbreviated as MOCVD) and a method for producing the same. .

[0002]

2. Description of the Related Art Conventionally, as a raw material for forming a copper thin film by the MOCVD method, Japanese Unexamined Patent Publication (Kokai) No. 5-59551 discloses a formula (α).

[0003]

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(Vinyltrimethylsilane)
(1,1,1,5,5,5-hexafluoro-2,4-
Β-diketonate copper (I) complexes consisting of pentanedionato) copper (I) are well known.

However, the β-diketonate copper (I) complex of the above formula (α) uses vinyltrimethylsilane as a ligand. Further, a β-diketonate copper (I) complex using an allene compound as a ligand has not been hitherto known.

[0006]

From the above-mentioned viewpoints, the present inventors have conducted research to find a novel β-diketonate copper (I) complex having an allene compound as a ligand, and as a result, the following formula (1) ) And the β-diketonate copper (I) complex represented by the formula (2).

[0007]

That is, the present invention provides a method of formula (1)

[0008]

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(Wherein, R ₁ , R ₂ , R ₃ and R ₄ may be the same or different and represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or (R ₅ ) ₃ Si. , R ₁ and R ₂
It may be a 6-membered ring, or may be an 8- to 10-membered ring by R ₂ and R ₃ . R ₅ represents a linear or branched alkyl group having one or two or more of the carbon atoms 1-4. Formula (2) having an allene compound represented by formula (I) as a ligand (L)

[0010]

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(In the formula, R ₆ and R ₇ may be the same or different, and may be a straight-chain or branched alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or 1 to 4 carbon atoms.
4 represents a linear or branched fluorine-substituted alkyl group. R
₈ represents a hydrogen atom or a fluorine atom. L represents the equation (1). Β-diketonate copper (I) represented by
The present invention relates to a complex and a method for producing the complex.

[0012]

Next, the present invention will be described in detail.

Β-diketonate copper (I) complex in formula (2)
With respect to the allene compound formula (1) which is a ligand (L) of
R₁, R_Two, R_Three, R_FourAs H, Me, Et, n-P
r, n-Bu, i-Pr, i-Bu, s-Bu, t-B
u, Me_ThreeSi, Et_ThreeSi, n-Pr_ThreeSi, n-Bu_Three
Si, i-Pr_ThreeSi, i-Bu_ThreeSi, s-Bu_ThreeS
i, t-Bu_ThreeSi, Me_Two(Et) Si, Me_Two(N-
Pr) Si, Me_Two(N-Bu) Si, Me_Two(I-P
r) Si, Me_Two(I-Bu) Si, Me_Two(S-Bu)
Si, Me_Two(T-Bu) Si, Et_Two(Me) Si, E
t_Two(N-Pr) Si, Et_Two(N-Bu) Si, Et_Two
(I-Pr) Si, Et_Two(I-Bu) Si, Et_Two(S
-Bu) Si, Et_Two(T-Bu) Si, n-Pr_Two(M
e) Si, n-Pr_Two(Et) Si, n-Pr_Two(I-P
r) Si, n-Pr_Two(N-Bu) Si, n-Pr_Two(S
-Bu) Si, n-Pr_Two(T-Bu) Si, n-Bu_Two
(Me) Si, n-Bu_Two(Et) Si, n-Bu_Two(N
-Pr) Si, n-Bu_Two(I-Pr) Si, n-Bu_Two
(I-Bu) Si, n-Bu_Two(S-Bu) Si, n-
Bu_Two(T-Bu) Si, i-Pr_Two(Me) Si, i-
Pr_Two(Et) Si, i-Pr_Two(N-Pr) Si, i-
Pr_Two(N-Bu) Si, i-Pr_Two(S-Bu) Si,
i-Pr_Two(T-Bu) Si, i-Bu_Two(Me) Si,
i-Bu_Two(Et) Si, i-Bu_Two(N-Pr) Si,
i-Bu_Two(N-Bu) Si, i-Bu_Two(I-Pr) S
i, i-Bu_Two(S-Bu) Si, i-Bu_Two(T-B
u) Si, s-Bu_Two(Me) Si, s-Bu_Two(Et)
Si, s-Bu_Two(N-Pr) Si, s-Bu _Two(N-B
u) Si, s-Bu_Two(I-Pr) Si, s-Bu_Two(I
-Bu) Si, s-Bu_Two(T-Bu) Si, t-Bu_Two
(Me) Si, t-Bu_Two(Et) Si, t-Bu_Two(N
-Pr) Si, t-Bu_Two(N-Bu) Si, t-Bu_Two
(I-Pr) Si, t-Bu_Two(I-Bu) Si or
t-Bu_Two(S-Bu) Si.

Further, there may be mentioned those wherein R ₁ and R ₂ are bonded to form a cyclopropane ring, a cyclobutane ring, a cyclopentane ring or a cyclohexane ring.

And those in which R ₁ and R ₃ are bonded to form a cyclooctane ring, a cyclononane ring or a cyclodecane ring.

Next, in the β-diketonate copper (I) complex formula (2), R ₆ and R ₇ are CF ₃ , C ₂ F ₅ ,
_{n-C 3 F 7, i} -C 3 F 7, n-C 4 F 9, Me, Et, n
-Pr, n-Bu, i-Pr, i-Bu, s-Bu, t
-Bu, MeO, EtO, n-PrO, n-BuO, i
—PrO, i-BuO, s-BuO or t-BuO. Then, as the R _8, H or F and the like.

Here, the β-diketonate copper (I) of the present invention is used.
The method for producing the complex will be described with reference to Reaction Formula (A) and Reaction Formula (B).

[0018]

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(In the reaction formula (A), in the formula (1), R
₁ , R ₂ , R ₃ and R ₄ may be the same or different,
Hydrogen atom, alkyl group having 1 to 4 carbon atoms or (R ₅ ) ₃ S
represents i. Further, R ₁ and R ₂ may form a 3- to 6-membered ring, and R ₂ and R ₃ may form a 8- to 10-membered ring. R
₅ represents one or more linear or branched alkyl groups having 1 to 4 carbon atoms.

In the formula (3) or (4), R ₉ ,
R ₁₀ may be the same or different, and may be a linear or branched alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a linear or branched fluorine-substituted alkyl group having 1 to 4 carbon atoms. Represents R ₁₁ represents a hydrogen atom or a fluorine atom.

In the formula (2), R ₆ and R ₇ may be the same or different, and may be a straight-chain or branched alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or 1-carbon atom. Represents a straight-chain or branched fluorine-substituted alkyl group. R ₈ represents a hydrogen atom or a fluorine atom. Also,
L represents formula (1). In the reaction represented by the reaction formula (A), the allene compound formula (1) and the enol compound formula (3) or the carbonyl compound formula (4) (the formula (4) is a tautomer of the formula (3)) (I) CuX as a compound
By reacting with the formula (5), and optionally in the presence of a base (for example, an inorganic base such as sodium hydride, potassium hydride, sodium amide, potassium tert-butoxide, potassium carbonate, etc.), the distribution of the allene compound is reduced. Β-diketonate copper (I) complex can be synthesized.

Here, the copper (I) compound is Cu ₂ O, C
uF, CuCl, CuBr, CuI, CuOAc, CuC
N, CuSCN, CuOTf and the like.

As shown in the reaction formula (B), the enol compound formula (3) is a tautomer of the carbonyl compound formula (4).

The molar ratio of the allene compound to the enol compound can be arbitrarily set, but the preferred range of the enol compound to the allen compound is equimolar or a ratio close to equimolar, for example, 0.5 to 1.5 moles. .

Although the molar ratio of the allene compound to the copper (I) compound can be arbitrarily set, the preferable range for the allene compound is an equimolar to excess molar ratio of copper metal atoms in the copper (I) compound, for example, 0. 0.5 to 3 times mol. The molar ratio of the base to the allene compound can also be arbitrarily set, but a preferred range is from equimolar to excess, for example, 0.5 to 3 moles.

The reaction temperature is not particularly limited, but it can be usually in the range of -110 ° C to the boiling point of the solvent used in the reaction. As a solvent that can be used, a solvent that does not participate in the reaction is preferable, and hydrocarbons (eg, hexane, pentane, benzene, toluene, etc.), ethers (eg, diethyl ether, monoglyme, isopropyl ether, tetrahydrofuran,
1,4-dioxane, etc.) and halogenated hydrocarbons (eg, dichloromethane, chloroform, dichloroethane, etc.) can be used.

The β-diketonate copper (I) complex of the present invention is represented by M
It is useful as a compound for forming a copper thin film by the OCVD method.

[0028]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

Example 1 In a nitrogen atmosphere, 30 mL of dry dichloromethane sufficiently degassed and replaced with nitrogen was poured into 3.0 g of copper (I) oxide to form a suspension solution. With vigorous stirring, 1.77 g of 1-methyl-1- (trimethylsilyl) arene was added, and then 3.2 g of 1,1,1,5,5,5-hexafluoro-2,4-pentanedione was slowly added with a dropping funnel. added. After stirring the reaction solution for 12 hours, it was filtered under a nitrogen atmosphere, and the filtrate was concentrated under reduced pressure at room temperature to obtain a green liquid. This is purified by column chromatography, and the formula (6)

[0030]

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Having 1-methyl-1- (trimethylsilyl) arene as a ligand, [1-methyl-
1- (trimethylsilyl) arene] (1,1,1,5,
5,5-hexafluoro-2,4-pentanedionato)
4.2 g of copper (I) were obtained as a yellow liquid.

The obtained β-diketonate copper (I) complex was identified by ¹ H-NMR and ¹³ C-NMR.

¹ H-NMR (δ, CDCl ₃ ) 0.19
(S, 9H), 1.97-1.99 (m, 3H), 4.
14-4.16 (m, 2H), 6.15 (s, 1H).

¹³ C-NMR (δ, CDCl ₃ ) -2.2
9 (3C), 17.09, 51.00, 90.21, 9
6.13, 117.69 (q, J _CF = 283.7 Hz,
2C), 173.87, 178.33 (q, J _CCF = 3
4.5 Hz, 2C).

In order to evaluate the vaporization characteristics of the obtained β-diketonate copper (I) complex, a thermogravimetric curve (heating rate 1
0 ° C / min. , Under a nitrogen atmosphere)
It was found to be extremely volatile and had good vaporization properties. 140-164 ° C.

Example 2 Under a nitrogen atmosphere, 30 mL of dry dichloromethane sufficiently degassed and replaced with nitrogen was poured into 3.0 g of copper (I) oxide to form a suspension solution. 1.72 g of 1,2-cyclononadiene was added with vigorous stirring, followed by 1,1,1,5,5,5-hexafluoro-2,4.
3.23 g of pentanedione were slowly added with a dropping funnel. After stirring the reaction solution for 4 hours, it was filtered under a nitrogen atmosphere, and the filtrate was concentrated under reduced pressure at room temperature to obtain a green liquid.

This is produced by column chromatography and has the formula (7)

[0038]

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(1,2-cyclononadiene) having 1,2-cyclononadiene represented by the following formula:
(1,1,1,5,5,5-hexafluoro-2,4-
5.63 g of pentanedionato) copper (I) were obtained as a yellow solid.

The obtained β-diketonate copper (I) complex was identified by ¹ H-NMR and ¹³ C-NMR.

¹ H-NMR (δ, CDCl ₃ ) 1.38-
1.77 (m, 8H), 2.06-2.24 (m, 4
H), 5.26-5.32 (m, 2H), 6.10.
(S, 1H).

¹³ C-NMR (δ, CDCl ₃ ) 23.6
5,25.49,28.44,88.28,90.6
1,118.65 (q, J _CF = 284.1 Hz, 2
C), 173.83, 178.63 (q, J _CCF = 3
4.6 Hz, 2C).

In order to evaluate the vaporization characteristics of the obtained β-diketonate copper (I) complex, a thermogravimetric curve (heating rate 1
0 ° C./min. , Under a nitrogen atmosphere), the melting point was 46.8 ° C and the boiling point was 195.6 ° C.

Example 3 In the same manner as in Example 2, 3.0 g of copper (I) oxide, 1.30 g of 1,2-heptadiene and 1,1,1,5,5,5-hexafluoro-2 From 3.23 g of, 4-pentanedione, formula (8)

[0045]

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(1,2-heptadiene) (1,1,1) having 1,2-heptadiene represented by the following formula:
2.82 g of 1,5,5,5-hexafluoro-2,4-pentanedionato) copper (I) were obtained as a yellow liquid.

¹ H-NMR (δ, CDCl ₃ ) 0.89
(T, J = 7.3 Hz, 3H), 1.30-1.42
(M, 2H), 1.42-1.54 (m, 2H), 2.
15-2.27 (m, 2H), 4.33-4.40
(M, 2H), 5.45-5.55 (m, 1H), 6.
13 (s, 1H).

¹³ C-NMR (δ, CDCl ₃ ) 13.9
5,22.46,31.50,31.70,55.7
2,90.76,92.44,117.96 (q, J
_CF = 283.7 Hz, 2C), 165.80, 17
8.85 (q, J _CCF = 34.5 Hz, 2C).

In order to evaluate the vaporization characteristics of the obtained β-diketonate copper (I) complex, a thermogravimetric curve (heating rate 1
0 ° C./min. , Under a nitrogen atmosphere), and found to have a boiling point of 150.0 ° C.

Example 4 In the same manner as in Example 2, 3.0 g of copper (I) oxide, 2.16 g of 1- (dimethyl-tert-butylsilyl) arene and 1,1,1,5,5,5 −
From 3.23 g of hexafluoro-2,4-pentanedione, formula (9)

[0051]

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[1- (dimethyl-tert-butylsilyl) arene] (1,1, having 1- (dimethyl-tert-butylsilyl) arene as a ligand
3.47 g of 1,5,5,5-hexafluoro-2,4-pentanedionato) copper (I) were obtained as a yellow liquid.

¹ H-NMR (δ, CDCl ₃ ) 0.20
(S, 6H), 0.97 (s, 9H), 4.35 (d,
J = 4.0 Hz, 2H), 4.87 (t, J = 4.4H)
z, 1H), 6.15 (s, 1H).

¹³ C-NMR (δ, CDCl ₃ ) -5.4
0, 18.72, 26.61, 55.36, 69.5
0,90.93,117.94 (q, J _CF = 283.
8Hz, 2C), 159.51, 178.96 (q, J
_CCF = 34.8 Hz, 2C).

In order to evaluate the vaporization characteristics of the obtained β-diketonate copper (I) complex, a thermogravimetric curve (heating rate 1
0 ° C./min. , Under a nitrogen atmosphere), and found to have a boiling point of 140.0 ° C.

(Example 5) In the same manner as in Example 2, 3.0 g of copper (I) oxide, 1.54 g of 1- (tert-butyl) -2-methylarene and 1,1,1,5,5 From 3.23 g of, 5-hexafluoro-2,4-pentanedione,
Equation (10)

[0057]

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1- (tert-butyl) -2 represented by
[1- (ter) having -methylallene as a ligand.
t-butyl) -2-methylarene] (1,1,1,5,
5,5-hexafluoro-2,4-pentanedionato)
1.78 g of copper (I) were obtained as a yellow liquid.

¹ H-NMR (δ, CDCl ₃ ) 1.18
(S, 9H), 1.89-1.98 (m, 3H), 5.
30-5.40 (m, 2H), 6.11 (s, 1H).

¹³ C-NMR (δ, CDCl ₃ ) 18.4
2,30.41,36.41,79.79,90.7
7, 93.20, 117.94 (q, J _CF = 283.
8Hz, 2C), 150.16, 178.78 (q, J
_CCF = 34.9 Hz, 2C).

In order to evaluate the vaporization characteristics of the obtained β-diketonate copper (I) complex, a thermogravimetric curve (heating rate 1
0 ° C./min. , Under a nitrogen atmosphere), and found to have a boiling point of 147.0 ° C.

(Example 6) Under a nitrogen atmosphere, 30 mL of dry dichloromethane sufficiently degassed and replaced with nitrogen was poured into 3.0 g of copper (I) oxide to form a suspension solution. With vigorous stirring, 0.96 g of 1,1-dimethylallene was added.
3.2 g of 1,1,5,5,5-hexafluoro-2,4-pentanedione was slowly added with a dropping funnel. Reaction solution 12
After stirring for an hour, the mixture was filtered under a nitrogen atmosphere, and the filtrate was concentrated under reduced pressure at room temperature to obtain a green liquid.

This was purified by column chromatography to obtain the compound of the formula (11)

[0064]

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(1,1-dimethylallene) (1,1,1,5,5) having 1,1-dimethylallene represented by the following formula:
2.3 g of 5,5-hexafluoro-2,4-pentanedionato) copper (I) were obtained as a pale yellow solid.

The obtained β-diketonate copper (I) complex was identified by ¹ H-NMR and ¹³ C-NMR.

¹ H-NMR (δ, CDCl ₃ ) 1.96
(T, J = 2.8 Hz, 6H), 4.16 (t, J =
2.8 Hz, 2H), 6.16 (S, 1H).

¹³ C-NMR (δ, CDCl ₃ ) 22.6
3 (2C), 50.03, 90.24, 108.41,
117.75 (q, J _CF = 284.9 Hz, 2C),
175.10, 178.40 (q, J _CCF = 34.7
Hz, 2C). (Example 7) Under a nitrogen atmosphere, 30 mL of dry dichloromethane sufficiently degassed and replaced with nitrogen was poured into 3.0 g of copper (I) oxide to form a suspension solution. 1,1,3,3-
1.35 g of tetramethylarene was added, followed by 1,1,1,
3.2 g of 5,5,5-hexafluoro-2,4-pentanedione
Was slowly added with a dropping funnel. After stirring the reaction solution for 12 hours, it was filtered under a nitrogen atmosphere, and the filtrate was concentrated under reduced pressure at room temperature to obtain a green liquid. This was purified by column chromatography, and the formula (12)

[0069]

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(1,1,3,3-tetramethylarene) (1,1,1,3,5,5,5) having 1,1,3,3-tetramethylarene represented by the following formula: 3.8 g of -hexafluoro-2,4-pentanedionato) copper (I) were obtained as a yellow solid.

The obtained β-diketonate copper (I) complex was identified by ¹ H-NMR and ¹³ C-NMR.

¹ H-NMR (δ, CDCl ₃ ) 2.00
(S, 12H), 6.18 (s, 2H).

¹³ C-NMR (δ, CDCl ₃ ) 24.8
4 (4C), 90.50 (2C), 93.25 (2
C), 117.81 (q, J _CF = 285.3 Hz, 4
C), 145.33, 178.61 (q, J _CCF = 3
4.7 Hz, 4C). The β-diketonate copper (I) complex of the present invention synthesized according to the above-mentioned production method or Examples is prepared by converting the β-diketonate copper (I) complex synthesized in the above Examples to a ligand (L) which is an allene compound. Table 1 below includes Formula (1)], but the present invention is not limited by these.

[0074]

[Table 1]

[0075]

[Table 2]

[0076]

[Table 3]

[0077]

[Table 4]

[0078]

[Table 5]

[0079]

[Table 6]

[0080]

[Table 7]

[0081]

[Table 8]

[0082]

[Table 9]

[0083]

[Table 10]

[0084]

The present invention provides a novel β-diketonate copper (I) complex and a method for producing the same. The β-diketonate copper (I) complex of the present invention is useful as a compound for forming a copper thin film by MOCVD. It is.

Claims (2)

[Claims] (1) Formula (1) _{(Wherein, R 1, R 2, R} 3, R 4 , which may be identical or different, represent a hydrogen atom, 1 to 4 carbon atoms alkyl or (R _{5) 3} Si. In addition, R ₁ and may be constituted by R ₂ in the 3- to 6-membered ring, R ₂ and they become 8-10 membered ring with R ₃ good .R ₅ also one or two or more straight from 1 to 4 carbon atoms Having an allene compound represented by the following formula (2) as a ligand (L): (Wherein, R ₆ and R ₇ may be the same or different, and are a straight-chain or branched alkyl group having 1 to 4 carbon atoms,
4 represents an alkoxy group or a linear or branched fluorine-substituted alkyl group having 1 to 4 carbon atoms. R ₈ represents a hydrogen atom or a fluorine atom. L represents the equation (1). Β) -diketonate copper (I) complex represented by the formula: 2. Formula (1) _{(Wherein, R 1, R 2, R} 3, R 4 , which may be identical or different, represent a hydrogen atom, 1 to 4 carbon atoms alkyl or (R _{5) 3} Si. In addition, R ₁ and may be constituted by R ₂ in the 3- to 6-membered ring, R ₂ and they become 8-10 membered ring with R ₃ good .R ₅ also one or two or more straight from 1 to 4 carbon atoms A chain or branched alkyl group) and a compound represented by the formula (3): (Wherein R ₉ and R ₁₀ may be the same or different,
A linear or branched alkyl group having 1 to 4 carbon atoms, 1 carbon atom
Represents an alkoxy group having 1 to 4 carbon atoms or a linear or branched fluorine-substituted alkyl group having 1 to 4 carbon atoms. R ₁₁ represents a hydrogen atom or a fluorine atom. Wherein the enol compound of formula (2) is reacted in the presence of a copper (I) compound. (Wherein, R ₆ and R ₇ may be the same or different, and are a straight-chain or branched alkyl group having 1 to 4 carbon atoms,
4 represents an alkoxy group or a linear or branched fluorine-substituted alkyl group having 1 to 4 carbon atoms. R ₈ represents a hydrogen atom or a fluorine atom. L represents the equation (1). )), A method for producing a β-diketonate copper (I) complex.