JPH09124658A - Elimination of organometal - Google Patents

Abstract

PROBLEM TO BE SOLVED: To eliminate organometal(s) from the inside of apparatus(es) safely and completely in a simple operation by adding a Lewis base to the organometal(s). SOLUTION: A Lewis base (e.g. diethyl ether, dibutyl ether, methyl butyl ether, anisole, diphenyl ether, dimethoxyethane, ethylene glycol dimethyl ether, tetrahydrofuran, dioxane) is added to organometal(s) lying adhered and left inside apparatus(es) or piping(s) (e.g. dimethylaluminum hydride trimethylaluminum, triethylaluminum, aminoalane, trimethylgallium, triethylgallium) to eliminate the organometal(s). It is preferable that the amount of the Lewis base to be added be pref. >=0.01 (more pref. 0.01-10)wt.% based on the organometal (s).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for excluding organic metal, and more particularly to an organic metal excluding method characterized by adding a Lewis base, such as dimethyl aluminum hydride, trimethyl aluminum, Safely protect organic metals from organic metals such as triethylaluminum, amine alane, trimethylgallium, triethylgallium, trimethylindium, and triethylgallium, that is, devices or pipes where compounds that ignite in the air adhere and remain. In addition, the present invention provides a method of excluding organic metals that can be completely excluded.

[0002]

2. Description of the Related Art Since organic metal is ignited in the air, when dismantling a device in which the organic metal adheres and remains,
(1) A method of removing the remaining organic metal by heating the inside of the apparatus and the piping in advance to evaporate the organic metal, and vacuum suctioning this, (2) dissolving the organic metal and reacting with the organic metal A method of washing and removing with an organic solution such as hexane or heptane is considered.

However, (1) in the case of an organic metal such as dimethyl aluminum hydride having a high viscosity,
In many cases, it cannot be excluded only by heating and vacuum suction, and the organic metal remaining in the equipment and piping ignites.
Problems such as soiling of the device have been caused by decomposition products of organic metals due to overheating. In the method of washing with the organic solution of (2), it is difficult to wash the accumulated portion of the valve or the pipe, particularly the highly viscous organometal is difficult to dissolve, and the remaining organometal is ignited.
There is a problem such as the need for a system for introducing and recovering a washing liquid several tens to several hundreds times the amount of a trace amount of organic metal.

[0004]

In view of such circumstances, in view of the above circumstances,
The present inventors have conducted an intensive study for the purpose of finding a method that is easy to perform, safe and can completely exclude an organic metal from the inside of an apparatus.As a result, when adding a Lewis base to an organic metal, They have found that they are all satisfactory, and have completed the present invention.

[0005]

That is, the present invention provides a method for excluding organic metals, which is characterized by adding a Lewis base.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The organic metal targeted by the exclusion method of the present invention is an organic metal applied in a MOCVD device or the like, and the type thereof is not particularly limited, but for example, dimethyl aluminum hydride, trimethyl aluminum, triethyl aluminum, amine alane. , Trimethylgallium,
Compounds such as triethylgallium, trimethylindium, triethylgallium are mentioned, among which dimethylaluminum hydride.

The Lewis base added to the organic metal is specifically diethyl ether, dibutyl ether, methyl butyl ether, diphenyl ether, benzyl ether,
Dimethoxyethane, diethoxyethane, ethylene glycol dimethyl ether, tetrahydrofuran (hereinafter T
HF), dioxane, triethylamine, trioctylamine, dimethylpropylamine, dimethyldodecylamine, dimethylaminotrimethylsilane, dimethylallylamine, diisopropylethylamine, dimethylaniline, benzylethylaniline, tetramethylethylenediamine, tetramethyldiaminopropane, tetramethyl. Hexamethylenediamine, pyridine, dimethylaminopyridine, collidine, pyrazine, dimethylpyrazine, quinoline, isoquinoline, quinaldine, benzylmethylimidazole, dimethyl sulfide, diethyl sulfide, diphenyl sulfide, thiophene, triethylphosphine, triphenylphosphine, triethylarsine, etc. To be You may use these 1 type (s) or 2 or more types. Above all, the use of diethyl ether and THF is recommended.

These Lewis bases are about 0.
01% by weight or more, preferably about 0.01% by weight to about 10%
It is used in the range of wt%, but is not particularly limited to this range. Regarding the upper limit, when the amount of the organic metal is large, it may be heated by the heat of coordination with the Lewis base to cause boiling or decomposition, or the coordination compound of the organic metal and the Lewis base is usually a high boiling point and may be difficult to exclude. Since it is large, it is not preferable to use it at about 100% by weight. However, if the amount of the organic metal is small and there is no problem due to the heat of coordination, it is possible to wash even with 100% by weight or more of Lewis base.

Hereinafter, the exclusion method of the present invention will be described with reference to the drawings, but the method is merely an example and does not limit the scope of application of the organometallic exclusion method of the present invention. FIG. 1 shows an example in which a Lewis base container and an organic metal recovery container are arranged in a generally known organic metal thin film forming apparatus for the purpose of carrying out the present invention. In the figure, 1 is an organic metal container, 2 is an organic metal thin film forming apparatus (hereinafter referred to as MOCVD apparatus), 3 is a Lewis base container, 4 is an organic metal recovery container, 5
10 to 10 are valves, and 11 is a vacuum suction device.

In the apparatus shown in FIG. 1, the valve 5 and the thin film forming apparatus 2 arranged on the upper part of the organic metal container 1 are arranged in the same manner as in a generally known method for forming a metal thin film on a substrate using an organic metal. Open the valve 6 installed at the entrance to open the valve 9
More inert gas such as hydrogen, argon, nitrogen is introduced,
Introduce organic metal into the thin film forming apparatus 2 via a pipe,
A metal thin film is formed on a substrate in the device. Usually, when a small amount of organic metal is introduced, heating or bubbling is also used to cause the inert gas to accompany the organic metal. However, when a large amount of organic metal is introduced, the organic metal remains as a liquid in the thin film forming apparatus 2. Introduce. The present invention is particularly effective in excluding the latter, and FIG. 1 shows an example of the latter.

After forming the metal thin film on the substrate, in the conventional method, the valves 5 and 6 are closed and the inside of the pipe is heated to dissolve and volatilize and remove the organic metal remaining in the pipe, or The inside of the pipe was washed with a solution capable of dissolving the above, such as hexane and heptane. In the present invention, the Lewis base container 3 is installed so that the Lewis base can be introduced into the pipe connecting the organometallic container 1 and the thin film forming apparatus 2 via the valve 7. Then, the Lewis base container 3
A valve 10 is arranged at the upper part, and a predetermined amount of Lewis base is supplied from the valve 10 into the container 3. On the other hand, an organic metal recovery container 4 having a vacuum suction device 11 is arranged via a valve 8 in a pipe connecting the organic metal container 1 and the thin film forming apparatus 2.

The method of exclusion in the apparatus is not particularly limited, but the following procedure can be carried out. The valve 7 is closed, a predetermined amount of Lewis base is supplied from the valve 10 into the container 3, and the valve 10 is closed. Valves 5, 6 and 8 are closed and valve 7 is opened to introduce the Lewis base into the pipe. The valve 7 is closed, and the valve 8 is opened while vacuum suction is performed by the vacuum suction device 11 provided in the organic metal recovery container 4.
The organic metal in the pipe is recovered in the organic metal recovery container 4. Further, the operations of to are repeated several times depending on the degree of washing.

During the cleaning, the valves 5 to 8 are closed, the piping between them is heated, and while the vacuum suction device 11 provided in the organic metal recovery container 4 performs vacuum suction, the valve 8 is opened to open the organic metal recovery container. It is also possible to collect the organic metal in the pipe in advance in 4. In this case, the heating temperature of the pipe may be a temperature below the decomposition temperature of the organic metal. Although the organic metal recovery container 4 may be at room temperature, it is preferable to cool the organic metal recovery container 4 because organic metal or the like does not escape to the vacuum suction device 11 side. By carrying out such an operation, it is possible to easily wash and remove the organic metal remaining and adhering not only to the vessel wall in the pipe but also to the reservoir of the pipe and the gap between the valves.

[0014]

EFFECTS OF THE INVENTION According to the method of removing an organic metal of the present invention, the liquid pool portion of a pipe or a valve, which has been difficult to wash in the past, can be easily washed and removed. Metal-filling work such as filling metal and MO
Replacement of metalorganic container in CVD equipment or MOC
There is no effect of ignition and smoke when the pipe is disassembled, which is caused by switching the raw material organic metal used in the VD device, and it is possible to safely work.

[0015]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the scope of the present invention is not limited to the examples. The apparatus shown in FIG. 1 was used in the examples.

Example 1 A commercially available DMAH (manufactured by Sumitomo Chemical Co., Ltd.) in the organometallic container 1 was introduced with argon from a valve 9 to obtain 0.2 kg /
Pressurize to cm ² , open valves 5 and 6 and DMAH
Is supplied to the MOCVD apparatus 2, and then the valve 5 and
After closing 6 and 9, the vacuum suction device 11 was operated, the valve 8 was opened, and the DMAH remaining in the pipe was recovered in the recovery container 4. At that time, the recovery container 4 was cooled to −70 ° C. with hexane / dry ice, and the pipe was heated to 50 ° C. Then, 0.1 ml of THF was introduced from the valve 10 into the Lewis base container 3 to close the valve 10, and then the valve 8 was closed.
The valve 7 was opened and THF was introduced into the pipe. After that, the valve 7 was closed and the valve 8 was opened again to collect the organic metal in the recovery tank 4. After repeating the operation of introducing THF and the operation of recovering the organic metal three times, the pipes 5 and 6
However, no white smoke was observed in any of the pipes.

COMPARATIVE EXAMPLE 1 Without using THF, the same exclusion procedure as in Example 1 was carried out, and then the pipes 5 and 6 were removed. As a result, ignition was caused by an organic metal from both pipes.

COMPARATIVE EXAMPLE 2 Except that 0.1 ml of THF was replaced with 10 ml of heptane, the same exclusion procedure as in Example 1 was carried out, and then pipes 5 and 6 were used.
When the pipe was removed, white smoke was generated from the organic metal from all the pipes.

[Brief description of the drawings]

FIG. 1 shows an application example of an organic metal exclusion method.

[Explanation of symbols]

 1: Organometallic container 2: Organometallic thin film forming device 3: Lewis base container 4: Organometallic recovery container 5: Valve 6: Valve 7: Valve 8: Valve 9: Valve 10: Valve 11: Vacuum suction device

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical indication C11D 7/36 C11D 7/36 C23C 16/44 C23C 16/44 J

Claims (6)

[Claims] 1. A method for excluding organic metals, which comprises adding a Lewis base. 2. The method for excluding organic metal according to claim 1, wherein the organic metal is any one of dimethyl aluminum hydride, trimethyl aluminum, triethyl aluminum, amine alane, trimethyl gallium, triethyl gallium, trimethyl indium and triethyl gallium. 3. The method for excluding organic metal according to claim 1, wherein the organic metal is dimethyl aluminum hydride. 4. A Lewis base is diethyl ether, dibutyl ether, methyl butyl ether, anisole, diphenyl ether, benzyl ether, dimethoxyethane,
Diethoxyethane, ethylene glycol dimethyl ether, tetrahydrofuran, dioxane, triethylamine, trioctylamine, dimethylpropylamine, dimethyldodecylamine, dimethylaminotrimethylsilane, dimethylallylamine, diisopropylethylamine, dimethylaniline, benzylethylaniline, tetramethylethylenediamine, tetramethyl Diaminopropane, tetramethylhexamethylenediamine, pyridine, dimethylaminopyridine, collidine, pyrazine, dimethylpyrazine, quinoline, isoquinoline, quinaldine, benzylmethylimidazole, dimethyl sulfide, diethyl sulfide, diphenyl sulfide, thiophene, triethylphosphine, triphenylphosphine, Is it a group consisting of triethylarsine? How exclusion organometallic claim 1, wherein the at least one selected. 5. The method for excluding organic metal according to claim 1, wherein the Lewis base is diethyl ether or tetrahydrofuran. 6. The method for excluding organic metal according to claim 1, wherein the addition amount of the Lewis base to the organic metal is 0.01% by weight or more.