JP2006306682A - MANUFACTURING METHOD OF Ni(PF3)4 - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a manufacturing method which has a high yield, which permits mass-production, and further by which high purity Ni(PF<SB>3</SB>)<SB>4</SB>is obtained. <P>SOLUTION: The manufacturing method is a manufacturing method of Ni(PF<SB>3</SB>)<SB>4</SB>which is provided with a mixing step for mixing a compound exhibited by general formula [I]: [(R)<SB>n</SB>C<SB>5</SB>H<SB>5-n</SB>]<SB>2</SB>Ni (wherein R is hydrogen or a hydrocarbon group, n is an integer of 0-5, and when there are two or more of R, all of R may be the same or different) with a solvent having a boiling point of 100°C or higher, a reacting step for mixing the mixture obtained after the mixing step with PF<SB>3</SB>and reacting them, and an isolating step for isolating Ni(PF<SB>3</SB>)<SB>4</SB>produced after the reacting step therefrom. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

The present invention relates to a method for producing Ni (PF ₃ ) ₄ .

Ni (PF ₃ ) ₄ is promising as a raw material for forming Ni-based metals, particularly Ni-based thin films. If a large amount of Ni (PF ₃ ) ₄ is obtained in a high yield, Ni (PF ₃ ) is an industrial method for forming a Ni-based thin film having high functionality and high coverage. ₄ is expected to be used.

However, an industrial production method for Ni (PF ₃ ) ₄ has not been established.
At the laboratory level, a method of reacting biscyclopentadienyl nickel [C ₅ H ₅ ] ₂ Ni with PF ₃ has been proposed.
[C ₅ H ₅ ] ₂ Ni + PF ₃ → Ni (PF ₃ ) ₄

However, the yield of Ni (PF ₃ ) ₄ by the method shown in this reaction formula is low. For example, it is about several percent. Therefore, this method is expensive and is not an industrial method suitable for mass production.

If an Ni film having a high purity is to be formed, the purity of Ni (PF ₃ ) ₄ must be high.
However, in the above method, there is a problem that organic substances derived from [C ₅ H ₅ ] ₂ Ni as a raw material are mixed.

Therefore, the first problem to be solved by the present invention is to provide a method for producing Ni (PF ₃ ) ₄ that has a high yield and can be mass-produced.

The second problem to be solved by the present invention is to provide a production method for obtaining highly pure Ni (PF ₃ ) ₄ .

While eagerly pursuing research to solve the above-mentioned problems, the present inventor has dissolved alkylcyclopentadienyl nickel in a solvent having a boiling point of 100 ° C. or higher, and then has said alkylcyclopentadienyl nickel and PF. _The reaction with ₃ led to the finding that the yield was improved.

As a result of continuing further research, when nonpolar solvents such as hydrocarbons are used, organic substances derived from cyclopentadienylnickel [C ₅ H ₅ ] ₂ Ni are very rarely mixed. I understand.

Furthermore, it has been found that organic impurities can be removed by washing crude Ni (PF ₃ ) ₄ containing organic impurities with a nonpolar solvent typified by hydrocarbon.

The present invention has been achieved based on such knowledge.
That is, the subject is a method for producing Ni (PF ₃ ) ₄ ,
A mixing step of mixing one or two or more compounds selected from the group of compounds represented by the following general formula [I] with a solvent having a boiling point of 100 ° C. or higher;
A reaction step of mixing and reacting the mixture and PF ₃ after the mixing step;
After the reaction step, it is solved generated Ni a (PF _{3) 4} by the manufacturing method of Ni (PF _{3) 4,} characterized in that comprises the isolation step of isolating.
Formula [I]
[(R) _n C ₅ H _5-n ] ₂ Ni
(However, R is H or a hydrocarbon group, and n is an integer of 0 to 5. When there are two or more Rs, all Rs may be the same or different.)

In particular, a method for producing Ni (PF ₃ ) ₄ , comprising:
A mixing step of mixing one or two or more compounds selected from the group of compounds represented by the following general formula [Ia] with a solvent having a boiling point of 100 ° C. or higher;
A reaction step of mixing and reacting the mixture and PF ₃ after the mixing step;
After the reaction step, it is solved generated Ni a (PF _{3) 4} by the manufacturing method of Ni (PF _{3) 4,} characterized in that comprises the isolation step of isolating.
Formula [Ia]
[(R) _n C ₅ H _5-n ] ₂ Ni
(However, R is H or an alkyl group, and n is an integer of 0 to 5. When there are two or more Rs, all Rs may be the same or different.)

Furthermore, a method for producing Ni (PF ₃ ) ₄ , comprising:
A mixing step of mixing one or two or more compounds selected from the group of compounds represented by the following general formula [Ib] with a solvent having a boiling point of 100 ° C. or higher;
A reaction step of mixing and reacting the mixture and PF ₃ after the mixing step;
After the reaction step, it is solved generated Ni a (PF _{3) 4} by the manufacturing method of Ni (PF _{3) 4,} characterized in that comprises the isolation step of isolating.
Formula [Ib]
[(R) _n C ₅ H _5-n ] ₂ Ni
(However, R is H or an alkyl group, and n is 0 or 1.)

In particular, a method for producing Ni (PF ₃ ) ₄ , comprising:
A mixing step of mixing one or two or more compounds selected from the group of compounds represented by the following general formula [Ic] with a solvent having a boiling point of 100 ° C. or higher;
A reaction step of mixing and reacting the mixture and PF ₃ after the mixing step;
After the reaction step, it is solved generated Ni a (PF _{3) 4} by the manufacturing method of Ni (PF _{3) 4,} characterized in that comprises the isolation step of isolating.
Formula [Ic]
[(R) _n C ₅ H _5-n ] ₂ Ni
(However, R is H or an alkyl group having 7 or less carbon atoms, and n is 0 or 1.)

In the present _invention, among the _{[(R) n C 5 H} 5-n] 2 Ni, [C 5 H 5] 2 Ni, [(CH 3) C 5 H 4] 2 Ni, [(C 2 H 5 _{) C 5 H 4] 2 Ni} , is _{[(i-C 3 H 7} ) C 5 H 4] 2 Ni, [(n-C 4 H 9) C 5 H 4] 2 that Ni is particularly preferred.

  In the present invention, the solvent is preferably a nonpolar solvent. Of these, one or more compounds (solvents) selected from the group consisting of nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane and hexadecane are preferred.

In the present invention, the isolation step is performed by atmospheric distillation or vacuum distillation. By such a distillation operation, Ni (PF ₃ ) ₄ is efficiently separated from the solvent, the raw material, and the reaction by-product.

In the present invention, prior to the isolation step (distillation step), it is preferable to separate crude Ni (PF ₃ ) ₄ with a nonpolar solvent having a boiling point of 100 ° C. or higher. That is, by washing crude Ni (PF ₃ ) ₄ with a nonpolar solvent having a boiling point of 100 ° C. or higher, Ni (PF ₃ ) ₄ is separated from the solvent, raw materials, and reaction byproducts. Therefore, by performing such a fractionation operation, subsequent distillation and purification can be performed efficiently.

In the present invention, it is preferable that the reaction step and the isolation step are performed simultaneously in parallel. That is, by doing so, the unreacted PF ₃ after the isolation step can be circulated and supplied to the reaction step, and the raw materials can be used efficiently.

Ni (PF ₃ ) ₄ is obtained in high yield. And it can be obtained in large quantities, easily and at a low cost. Furthermore, highly pure Ni (PF ₃ ) ₄ is obtained.

The present invention is a method for producing Ni (PF ₃ ) ₄ . And it has the mixing process which mixes the compound represented with the following general formula [I], and the solvent whose boiling point under 1 atmosphere is 100 degreeC or more. And, after the mixing step, mixing the mixture with PF _3, having a reaction step of reacting. Further, after the reaction step, with the resulting Ni (PF _{3) 4} the isolation step of isolating.
Formula [I]
[(R) _n C ₅ H _5-n ] ₂ Ni
(However, R is hydrogen or a hydrocarbon group, and n is an integer of 0 to 5. When there are two or more Rs, all Rs may be the same or different.)

In the above general formula, a compound in which R is an alkyl group (in particular, an alkyl group having 7 or less carbon atoms) is preferable. n is preferably a compound of 0 or 1. Among these compounds, particularly preferred compounds are the following compounds. _{[C 5 H 5] 2 Ni} , [(CH 3) C 5 H 4] 2 Ni, [(C 2 H 5) C 5 H 4] 2 Ni, [(i-C 3 H 7) C 5 H 4 _{] 2 Ni, [(n-} C 4 H 9) C 5 H 4] 2 Ni.

The solvent used in the present invention has a boiling point of 100 ° C. or higher, but preferably has a boiling point of 110 ° C. or higher. Further, the boiling point is 123 ° C. or higher. In particular, it has a boiling point of 135 ° C. or higher, particularly 140 ° C. or higher. There is no particular restriction on the upper limit of the boiling point, that is, it can be a liquid under normal pressure, but is usually 400 ° C. or lower.
The preferred solvent used in the present invention is a nonpolar solvent.
Among the solvents used in the present invention, preferred solvents are the following compounds. Nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane.

The isolation step of the present invention is performed by atmospheric distillation or vacuum distillation.
In the present invention, prior to the isolation step (distillation step), fractionation of crude Ni (PF ₃ ) ₄ is performed with a nonpolar solvent having a boiling point of 100 ° C. or higher. That is, by washing crude Ni (PF ₃ ) ₄ with a nonpolar solvent having a boiling point of 100 ° C. or higher under 1 atm, Ni (PF ₃ ) ₄ is separated from the solvent, raw material, and reaction by-product. The

In the present invention, the reaction step and the isolation step are simultaneously performed in parallel. That is, by doing so, the unreacted PF ₃ after the isolation step can be circulated and supplied to the reaction step, and the raw materials can be used efficiently.

Hereinafter, specific examples will be described.
[Example 1]
FIG. 1 is a schematic view of a Ni (PF ₃ ) ₄ manufacturing apparatus. In the figure, 1 is a PF ₃ cylinder, 2 is a mixture of an alkylcyclopentadienyl nickel and a solvent, 3 is a PF ₃ inlet, 4 is a stirrer, 5 is a reaction temperature controller, 6 is a cooler, 7 is a cooling trap for collecting Ni (PF ₃ ) ₄ , 8 is a cooling trap for recovering PF ₃ , and 9 is a pressure regulator.
Then, the production of Ni (PF _{3) 4} using the apparatus of FIG. 1 were made. All the production was performed under a nitrogen atmosphere.

First, 95 g (0.5 mol) of biscyclopentadienyl nickel [C ₅ H ₅ ] ₂ Ni is partially dissolved and partially dispersed in 800 ml of dehydrated and degassed tetradecane, and kept at 90 ° C. with stirring. It was.

Then, after the inside of the apparatus to a negative pressure was blown PF ₃ gas in the mixture until the reaction system internal pressure is near atmospheric pressure. After a while, PF ₃ was consumed by the reaction, and the pressure in the system became negative again.

Therefore, PF ₃ gas was blown into the mixed solution again until the internal pressure of the reaction system became close to atmospheric pressure. Such a process was repeated several times.

After this, the reaction vessel was cooled to room temperature. The system was depressurized by the pressure adjusting device 9. Ni (PF ₃ ) ₄ distilled under reduced pressure was collected by a cooling trap 7 for collection. Further, PF ₃ was recovered by the cooling trap 8. The recovered PF ₃ was supplied to the cylinder 1 and reused. Then, the same operation was performed until [C ₅ H ₅ ] ₂ Ni was consumed.

The collected Ni (PF ₃ ) ₄ was transferred to a separatory funnel, and tetradecane was added thereto. Then, it was divided into an upper layer (tetradecane layer) and a lower layer (Ni (PF ₃ ) ₄ ).

The lower layer was washed 5 times with tetradecane.
After washing, the product was purified by an atmospheric distillation device.

The boiling point of this purified product was 68 ° C. In addition, C was not detected when this purified product was provided to the combustion-infrared absorption method. In consideration of detection accuracy, even if C is included, it is 0.01 wt% or less.
The yield in this example was 165.8 g. Therefore, the yield is 81%.

A nickel thin film was prepared by the chemical vapor deposition method using Ni (PF ₃ ) ₄ thus obtained. When the Ni film thus obtained was analyzed by SIMS analysis, C was not detected. Further, when the specific resistance of this Ni film was examined, it was 13 μΩ · cm.

[Example 2]
In Example 1, instead of [C ₅ H ₅ ] ₂ Ni, [(CH ₃ ) C ₅ H ₄ ] ₂ Ni was used in the same manner.
As a result, the same result as in Example 1 was obtained.

[Example 3]
In Example 1, instead of [C ₅ H ₅ ] ₂ Ni, [(C ₂ H ₅ ) C ₅ H ₄ ] ₂ Ni was used in the same manner.
As a result, the same result as in Example 1 was obtained.

[Example 4]
In Example _1, in place of the _{[C 5 H 5] 2 Ni} , using the _{[(i-C 3 H 7} ) C 5 H 4] 2 Ni, it was the same.
As a result, the same result as in Example 1 was obtained.

[Example 5]
In Example 1, instead of [C ₅ H ₅ ] ₂ Ni, [(n—C ₄ H ₉ ) C ₅ H ₄ ] ₂ Ni was used in the same manner.
As a result, the same result as in Example 1 was obtained.

[Examples 6 to 13]
In Example 1, in place of tetradecane, nonane, decane, undecane, dodecane, tridecane, pentadecane, and hexadecane were used in the same manner.
As a result, the same result as in Example 1 was obtained.

[Comparative Example 1]
In Example 1, diethyl ether (boiling point: 34.6 ° C.) was used in the same manner instead of tetradecane.
The yield of the obtained Ni (PF ₃ ) ₄ was 10%.
Further, a nickel thin film was prepared by the chemical vapor deposition method using Ni (PF ₃ ) ₄ obtained in this comparative example. When the Ni film thus obtained was analyzed by SIMS analysis, about 4% of C was detected. Further, since the Ni film of this comparative example was inferior in purity as compared with the Ni film of Example 1, its specific resistance was also inferior to that of Example 1.

[Comparative Example 2]
In Example 1, heptane (boiling point 98 ° C.) was used in the same manner instead of tetradecane.
However, separation from the solvent was difficult, and pure Ni (PF ₃ ) ₄ could not be obtained.

Schematic of Ni (PF ₃ ) ₄ manufacturing equipment

Explanation of symbols

1 PF ₃ cylinder 2 [C ₅ H ₅ ] ₂ Mixed solution of Ni and tetradecane 3 PF ₃ inlet 4 Stirrer 5 Reaction temperature controller 6 Cooler 7 Ni (PF ₃ ) ₄ Cooling trap 8 PF ₃ for collection Cooling trap 9 for recovery Pressure regulator
Representative Katsumi Udaka

Claims (8)

A method for producing Ni (PF ₃ ) ₄ , comprising:
A mixing step of mixing one or two or more compounds selected from the group of compounds represented by the following general formula [I] with a solvent having a boiling point of 100 ° C. or higher;
A reaction step of mixing and reacting the mixture and PF ₃ after the mixing step;
An isolation step for isolating the produced Ni (PF ₃ ) ₄ after the reaction step, and a method for producing Ni (PF ₃ ) ₄ .
Formula [I]
[(R) _n C ₅ H _5-n ] ₂ Ni
(However, R is H or a hydrocarbon group, and n is an integer of 0 to 5. When there are two or more Rs, all Rs may be the same or different.) The compound represented by the general formula [I] is [C ₅ H ₅ ] ₂ Ni, [(CH ₃ ) C ₅ H ₄ ] ₂ Ni, [(C ₂ H ₅ ) C ₅ H ₄ ] ₂ Ni, [ Ni (PF ₃ ) _{4 according} to claim 1, characterized in that it is (i-C ₃ H ₇ ) C ₅ H ₄ ] ₂ Ni, [(n-C ₄ H ₉ ) C ₅ H ₄ ] ₂ Ni. Production method. The method for producing Ni (PF ₃ ) _{4 according} to claim 1 or 2, wherein the solvent is a nonpolar solvent. The solvent is one or two or more compounds selected from the group consisting of nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, and hexadecane. A method for producing Ni (PF ₃ ) ₄ . The isolation step is performed by distillation under atmospheric pressure or reduced pressure, and Ni (PF ₃ ) ₄ is separated from the solvent, the raw material, and the reaction by-product. A method for producing Ni (PF ₃ ) ₄ . Isolation process, of any of claims 1 to claim 5, characterized in that it is carried out after the boiling was separated crude Ni (PF _{3) 4} in a nonpolar solvent than 100 ° C. Ni of (PF _{3) 4} Production method. The method for producing Ni (PF ₃ ) _{4 according to} any one of claims 1 to 6, wherein the reaction step and the isolation step are simultaneously performed in parallel. The method for producing Ni (PF ₃ ) _{4 according to} any one of claims 1 to 7, wherein unreacted PF ₃ after the isolation step is supplied to the reaction step.

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