JP2001199909A - Organic copper complex - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an organic copper complex for MOCVD, having <=60 deg.C melting point, excellent in heat stability at the time of vaporization, and capable of being prepared from an easily available ligand. SOLUTION: This organic copper complex is a compound containing a terpene as the ligand, and represented by the general formula (I) (wherein, R1 and R2 are each a 1-8C alkyl group or a 1-8C perfluoroalkyl group; R3 is H, F or a 1-8C perfluoralkyl group; and L is a monoterpene), and can satisfy the purpose.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organic copper complex suitable for use as a vapor deposition material when a copper thin film such as a semiconductor wiring is formed by metal organic chemical vapor deposition (hereinafter referred to as MOCVD). It is.

[0002]

2. Description of the Related Art As a raw material for forming a copper thin film by MOCVD, (vinyltrimethylsilane) (hexafluoroacetylacetonato) copper (I) represented by the following formula (II) is used.
A complex [hereinafter referred to as Cu (hfac) (tmvs)] is well known (JP-A-5-55951).

[0003]

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[0004]

The compound is a liquid at around room temperature, which is a property that is convenient for vaporization at a uniform rate. A decomposition reaction gradually occurs in the container. for that reason,
There is a problem that the vaporization rate varies with time.
Further, JP-A-7-70162 and JP-A-7-70163 disclose organocopper complexes having an acetylene compound having a trialkylsilyl group as a ligand. Because of the use of a child, there was a problem that manufacturing was difficult. An object of the present invention is to provide an organic copper complex for MOCVD, which has a melting point of 60 ° C. or lower, has excellent thermal stability during vaporization, and is prepared from a ligand which is easily available.

[0005]

Therefore, when a copper thin film was formed by MOCVD, research was conducted to find an organic copper complex having excellent thermal stability during vaporization. As a result, terpene was contained as a ligand. Wherein R ¹ and R ² are an alkyl group having 1 to 8 carbon atoms or a perfluoroalkyl group having 1 to 8 carbon atoms;
³ is an H, F atom or a perfluoroalkyl group having 1 to 8 carbon atoms, and L represents a monoterpene), which has been found to be an organic copper complex that has solved the above-mentioned problems, and has completed the present invention.

[0006]

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[0007]

BEST MODE FOR CARRYING OUT THE INVENTION In the general formula (I) shown above, R ¹ and R ² are CF ₃ groups, R ³ is an H atom, and the ligand L is represented by the formula (III) )-(+)-Limonene, when represented by formula (IV), ((R)-
(+)-Limonene) (1,1,1,5,5,5-hexafluoro-2,4-pentanedionato) copper (I) complex is obtained. The copper complex [hereinafter, Cu (hfac) (+ l
im) is a novel substance and is a yellow liquid near room temperature.

[0008]

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[0009]

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When (S)-(-)-limonene is used as the ligand L, the same complex ((S)-(-)-limonene) (1,1,1,5,5,5) is used. -Hexafluoro-
2,4-pentanedionato) copper (I) [hereinafter referred to as Cu (h
fac) (-lim)]. Also,
When a mixture of (+)-limonene and (−)-limonene in an arbitrary ratio or (±) -limonene is used, Cu (h)
fac) (+ lim) and Cu (hfac) (-lim)
Is obtained. These complexes are also novel substances.

In the above general formula (I), R ¹ and R ² are CF ₃ groups, R ³ is an H atom, and the ligand L is α
The complex represented by -terpinene [formula (V)] is (α-terpinene) (1,1,1,5,5,5-hexafluoro-
2,4-pentanedionato) copper (I), hereinafter referred to as Cu (h
fac) (αtp)] [Formula (VI)]. This complex is also a novel substance and exists as a yellow liquid near room temperature.

[0012]

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[0013]

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In the above general formula (I), when R ¹ and R ² are CF ₃ groups, R ³ is an H atom and the ligand L is terpinolene [formula (VII)], (VIII)
(Terpinolene) (1,1,1,5,5,5
-Hexafluoro-2,4-pentanedionato) copper (I) complex. This complex [hereinafter referred to as Cu (hfa
c) (tl)] is also a novel substance.

[0015]

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[0016]

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In the general formula (I), R ¹ and R ² represent C
When R ³ is an H atom in the F ₃ group and the ligand L is (+)-camphene [formula (IX)], ((+)-campphene) (1 , 1,1,5,5,5-hexafluoro-2,4-pentanedionato) copper (I) complex [hereinafter referred to as Cu (hfac) (+ cp)]. If (−)-camphene and (±) -camphene are used instead of (+)-camphene, Cu (h)
fac) (-cp) and Cu (hfac) (± cp) are obtained. These complexes are also novel substances.

[0018]

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[0019]

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Formula (I) which can be used in the present invention
Examples of the monoterpene represented by L include limonene ((+) form, (−) form, (±) form), terpinene (α form, β form, γ form), terpinolene, camphene ((+) Body, (-) body, (±) body), ferrandrene (α body, β body), sylvestrene ((+) body,
(−) Body, (±) body), karen (Δ ³ body, Δ ⁴ body), sabinene ((+) body, (−) body, (±) body), myrcene, ocimene, and the like.

[0021]

The organocopper complex of the present invention can be synthesized by reacting copper (I) oxide, a terpene compound and a β-diketone compound. As the terpene, an easily available one can be used. The product can be easily purified by ordinary column chromatography. Hereinafter, the method for producing the organocopper compound of the present invention will be described with reference to specific examples.

Example 1 This example relates to a compound represented by the formula (I) in which R ¹ and R ² are CF ₃ groups, R ³ is an H atom, and the monoterpene of the ligand L is α-terpinene. Organic copper complex Cu represented by (VI)
The synthesis of (hfac) (αtp) is exemplified. All reactions are performed under an argon atmosphere. 100c with argon substitution
c In a two-necked flask, 60 ml of dry hexane was taken, and 3.58 g (25.0 mmol) of copper (I) oxide was suspended. 3.41 g (25.0 mm) of α-terpinene was added to the suspension.
ol) and stirred at room temperature for 30 minutes.
5.20 g (25.0 mmol) of 1,5,5,5-hexafluoro-2,4-pentanedione was added dropwise. After completion of the dropwise addition, the mixture was reacted by stirring at room temperature for 2 hours, and unreacted copper oxide was filtered off under argon to obtain a yellow-green solution. By concentrating this solution, a crude compound was obtained as a yellow-green liquid. The crude product was subjected to column chromatography using silica gel as a filler under an argon atmosphere to obtain 6.05 g of the desired Cu (hfac) (αtp) (1
4.9 mmol, 60% yield) as a yellow liquid.

The identification of the organocopper compound was performed by NMR and elemental analysis. NMR (CDCl ₃ ): δ 1.06-1.08 (m 6H), 1.80 (s 3
H), 2.18-2.22 (m4H), 2.25-
2.35 (m1H), 5.57-5.62 (m2
H), 6.06 (s 1H) · Elemental _{analysis: C 15 H 17 F 6 O} 2 Cu measurement C: 44.9%, H: 4.27 %, Cu: 15
% Theoretical value C: 44.3%, H: 4.21%, Cu: 1
5.6% Melting point: -5 ° C

Further, the organic copper compound of the present invention was sealed in a glass ampule tube under reduced pressure and heated at 80 ° C. for 1 hour. As a result, a yellow liquid remained, and no visual alteration was observed.

Example 2 In this example, in the general formula (I), R ¹ and R ² are CF ₃ groups, R ³ is an H atom, and the monoterpene of the ligand L is
Cu (hfac) which is (R)-(+)-limonene
It is a synthesis example of (+ lim). 3.41 g (25.0 mm) of (R)-(+)-limonene instead of α-terpinene
ol) was performed in the same manner as in Example 1. Under an argon atmosphere, 6.63 g of Cu (hfac) (+ lim) of the present invention was obtained by a conventional column chromatography.
(16.3 mmol, 65% yield) was obtained. This compound was a yellow liquid at room temperature.

The identification of the organocopper complex was performed by NMR and elemental analysis. 1 H-NMR (CDCl ₃ ): δ1.59-1.66 (m 1H), 1.66 (s 3)
H), 1.84 (s 3H), 1.89-1.93 (m
1H), 2.03-2.04 (m3H), 2.18-
2.23 (m2H), 4.40-4.42 (m2
H), 5.37 (m1H), 6.08 (s 1H) · Elemental _{analysis: C 15 H 17 F 6 O} 2 Cu measurement C: 45.1%, H: 4.29 %, Cu: 15
% Theoretical value C: 44.3%, H: 4.21%, Cu: 1
5.6% Melting point: -5 ° C

When the organocopper compound of the present invention was sealed in a glass ampule tube under reduced pressure and heated at 80 ° C. for 1 hour, it remained a yellow liquid, and no deterioration was visually observed.

Example 3 In this example, in the general formula (I), R ¹ and R ² are CF ₃ groups, R ³ is an H atom, and L monoterpene is represented by (S) —
Cu (hfac) (-lim) which is (−)-limonene
Is exemplified. (S) instead of α-terpinene
The procedure was performed in the same manner as in Example 1 except that 3.41 g (25.0 mmol) of-(-)-limonene was used. Under an argon atmosphere, 6.30 g of Cu (hfac) (-lim) of the present invention (15.
(4 mmol, 62% yield). This compound was a yellow liquid at room temperature.

The identification of the organic copper compound was performed by NMR and elemental analysis. 1H-NMR (CDCl ₃ ): δ 1.62-1.68
(M 1H), 1.68 (s 3H), 1.86 (s 3
H), 1.94 (m1H), 2.06-2.09 (m
3H), 2.23-2.26 (m2H), 4.31-
4.34 (m2H), 5.36 (m1H), 6.09
(S 1H) · Elemental _{analysis: C 15 H 17 F 6 O} 2 Cu measurement C: 45.0%, H: 4.28 %, Cu: 15
% Theoretical value C: 44.3%, H: 4.21%, Cu: 1
5.6% Melting point: -5 ° C

When the organocopper compound of the present invention was sealed in a glass ampule tube under reduced pressure and heated at 80 ° C. for 1 hour, it remained a yellow liquid, and no visual alteration was observed at all.

Example 4 In this example, in the general formula (I), R ¹ and R ² are CF
An example in which (±) -limonene (= dipentene), which is most easily available as a monoterpene for L, is used, although R ³ is an H atom in ^three groups, is shown. The complex obtained is Cu (hfa
c) A mixture of (+ lim) and Cu (hfac) (− lim) in almost equivalent amounts, and Cu (hafc) (± li
m). The procedure was performed in the same manner as in Example 1 except that 3.41 g (25.0 mmol) of (±) -limonene (dipentene) was used instead of α-terpinene. Under an argon atmosphere, Cu was obtained by ordinary column chromatography.
(Hfac) (± lim) 6.41 g (15.8 mmol)
l yield 63%). This compound was a viscous yellow liquid at room temperature.

The identification of the organic copper compound was performed by NMR and elemental analysis. 1 H-NMR (CDCl ₃ ): δ1.59-1.68
(M 1H), 1.66 (s 3H), 1.84 (s 3
H), 1.89-1.94 (m1H), 2.03-
2.09 (m3H), 2.18-2.26 (m3H
H), 4.31-4.42 (m2H), 5.37 (m
1H), 6.08 (s 1H)

Elemental analysis: measured value of C ₁₅ H ₁₇ F ₆ O ₂ Cu C: 44.8%, H: 4.26%, Cu: 15
% Theoretical value C: 44.3%, H: 4.21%, Cu: 1
5.6% Melting point: -5 ° C

When the organocopper compound of the present invention was sealed in a glass ampule tube under reduced pressure and heated at 80 ° C. for 1 hour, it remained a yellow liquid and no alteration was visually observed.

Example 5 This example relates to an organic copper complex (γ) in which R ¹ and R ² are CF ₃ groups, R ³ is an H atom, and the monoterpene of L is γ-terpinene in the general formula (I). -Terpinene) (1,1,
1,5,5,5-hexafluoro-2,4-pentanedionato) copper (I) [hereinafter, Cu (hfac) (γtp)
This is exemplified. The procedure was performed in the same manner as in Example 1 except that 3.41 g (25.0 mmol) of γ-terpinene was used instead of α-terpinene. Under an argon atmosphere, Cu was obtained by ordinary column chromatography.
(Hfac) (γtp) 6.05 g (14.9 mmol)
Yield 60%). The compound was solid at room temperature and yellow.

This organic copper compound was identified by NMR. 1H-NMR (CDCl ₃ ): δ 1.10-1.12.
(M 6H), 1.86 (s 3H), 2.38 (m 1
H), 2.78 (m4H), 5.34 (m2H),
5.94 (s 1.4H) Melting point: 57-59 ° C

When the organocopper compound of the present invention was sealed in a glass ampule tube under reduced pressure and heated at 80 ° C. for 1 hour, it remained yellow and no deterioration was visually observed.

Example 6 In this example, in the general formula (I), Cu (hfac) (tl) in which R ¹ and R ² are a CF ₃ group, R ³ is an H atom and L monoterpene is terpinolene ) Is exemplified. Terpinolene 3.41 instead of α-terpinene
g (25.0 mmol), except that g (25.0 mmol) was used. Under an argon atmosphere, Cu (hfac) (tl) 4.1 was obtained by a conventional column chromatography.
9 g (10.3 mmol, 41% yield) were obtained. The compound was solid at room temperature and yellow.

This organic copper compound was identified by NMR. 1 H-NMR (CDCl ₃ ): δ 1.80 (s 3
H), 1.82 (s 3H), 1.89 (s 3H),
2.40-2.47 (m 4H), 2.97 (m 2
H), 5.28 (m1H), 6.06 (s1.5H) Melting point: 52-54 ° C

When the organocopper compound of the present invention was sealed in a glass ampoule tube under reduced pressure and heated at 80 ° C. for 1 hour, it remained yellow and no deterioration was visually observed.

Example 7 In this example, in the general formula (I), R ¹ and R ² are CF ₃ groups, R ³ is an H atom and L monoterpene is represented by (±)-
The synthesis of Cu (hfac) (± cp), which is a camphene, is illustrated. The same operation as in Example 1 was performed except that 3.41 g (25.0 mmol) of (±) -camphene was used instead of α-terpinene. Under an argon atmosphere, 6.43 g of the present invention was obtained by conventional column chromatography.
(15.8 mmol, 63% yield) was obtained. This compound was a yellow solid at room temperature.

This organic copper compound was identified by NMR. 1 H-NMR (CDCl ₃ ): δ 1.11 (s 3
H), 1.20 (s3H), 1.34-1.37 (m
2H), 1.45-1.48 (m1H), 1.72-
1.78 (m2H), 2.05 (m1H), 2.17
-2.21 (m1H), 2.72 (m1H), 4.1
3 (s 1H), 4.38 (s 1H), 6.09 (s
1H) Melting point: 56-58 ° C

The organic copper complex of the present invention, C
u (hfac) (αtp), Cu (hfac) (+ li
m), Cu (hfac) (-lim), Cu (hfa)
c) (± lim), Cu (hfac) (tl), Cu
(Hfac) (γtp) and Cu (hfac) (± c
In each of p), even when heated at 80 ° C. for 1 hour in a state sealed in a glass ampule tube under reduced pressure, the yellow color was maintained, and no deterioration was visually observed. On the other hand, a conventionally well-known organic copper complex C represented by the formula (II)
At 80 ° C., u (hfac) (tmvs) decomposes after 2 to 3 minutes, changes from yellow to black, and eventually copper is deposited on the glass wall. That is, it can be seen that all of the organocopper complexes of the present invention show more excellent stability to heating during vaporization than the conventionally known compound (II).

[0044]

Since the organocopper complex of the present invention has a sufficiently low melting point and excellent thermal stability, it is possible to supply a raw material with little change over time in the MOCVD method. In addition, since it is synthesized from a ligand which is easily available, the utility is high. That is, it can be effectively used for manufacturing a copper thin film requiring uniformity such as a semiconductor wiring material.

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Claims (5)

[Claims] 1. A compound represented by the following general formula (I) (Wherein R ¹ and R ^{2 each} have 1 to 1 carbon atoms)
An alkyl group having 8 carbon atoms or a perfluoroalkyl group having 1 to 8 carbon atoms, R ³ represents an H, F atom or 1 carbon atom;
~ 8 perfluoroalkyl groups, L represents a monoterpene). 2. The method according to claim 1, wherein R ¹ and R ² are CF ₃
An organic copper complex, wherein R ³ is an H atom. 3. The monoterpene represented by L is limonene [(+)-form, (-)-form, or any mixture thereof, or (±) -form]. 3. The organic copper complex according to 2. 4. The method according to claim 1, wherein the monoterpene represented by L is terpinene (α-form, β-form, or γ-form, or any mixture thereof) or terpinolene. Organic copper complexes. 5. The monoterpene represented by L is camphene ((+)-form, (-)-form, or any mixture thereof, or (±) -form). 3. The organic copper complex according to 2.