JPH09111299A - Cleaning liquid composition for organic metal exclusion - Google Patents

Abstract

(57) Abstract: A cleaning liquid composition capable of easily and safely excluding organic metals from inside a pipe is supplied. SOLUTION: A Lewis base such as diethyl ether or tetrahydrofuran is added to a solution such as hexane capable of dissolving an organic metal such as dimethyl aluminum hydride in an amount of 0.01
A cleaning liquid composition for organic metal exclusion, which comprises from 50% by weight to 50% by weight.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cleaning liquid composition for excluding organic metals, and more particularly to a cleaning liquid composition obtained by adding a Lewis base to a solution capable of dissolving an organic metal, and dimethylaluminum hydride. PROBLEM TO BE SOLVED: To provide a cleaning liquid composition for removing an organic metal, which can safely and completely remove an organic metal such as trimethylaluminum, trimethylgallium, and trimethylindium, that is, a device in which a compound that ignites in the air adheres and remains. It is a thing.

[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-sucking this, and (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, it is difficult to apply the method of (1) to organic metals with high boiling points, and (2)
When cleaning with an organic solution, it is difficult to clean the accumulated part of the valve and piping, especially high-viscosity organic metal or solid organic metal is difficult to dissolve, and when the device is disassembled, the remaining organic metal ignites due to insufficient exclusion. Then, there was a problem.

[0003]

In view of such circumstances, in view of the above circumstances,
The present inventors have made an intensive study for the purpose of finding a method of easily and safely excluding organic metal from the inside of the apparatus, and as a result, a specific substance is added to a solution capable of dissolving the organic metal to be present, When this was used as a cleaning liquid, it was found that all of the above objects could be satisfied, and the present invention was completed.

[0004]

That is, the present invention provides a cleaning liquid composition for removing an organic metal, which comprises a Lewis base in a solution capable of dissolving an organic metal.

[0005]

The present invention will be described in more detail below. The organic metal targeted by the cleaning liquid composition of the present invention is MO.
It is an organic metal applied in a CVD apparatus or the like, and the kind thereof is not particularly limited, but for example, dimethyl aluminum hydride (DMAH), trimethyl aluminum, triethyl aluminum, amine alane, trimethyl gallium, triethyl gallium, trimethyl indium or Triethylindium and the like can be mentioned, among others,
Dimethyl aluminum hydride can be mentioned.

The solution capable of dissolving an organic metal includes all compounds capable of dissolving an organic metal and does not react with the organic metal, specifically hydrocarbons, more specifically hexane, heptane, Dodecane, liquid paraffin, benzene, toluene, xylene and the like can be mentioned.

The Lewis base to be added to and mixed with a solution capable of dissolving an organic metal is specifically diethyl ether, dibutyl ether, methylbutyl ether, diphenyl ether, anisole, benzyl ether, dimethoxyethane, diethoxyethane, ethylene glycol dimethyl ether, tetrahydrofuran. (Hereinafter referred to as THF),
Dioxane, triethylamine, trioctylamine,
Dimethylpropylamine, dimethyldodecylamine, dimethylaminotrimethylsilane, dimethylallylamine, diisopropylethylamine, dimethylaniline,
Benzylethylaniline, tetramethylethylenediamine, tetramethyldiaminopropane, tetramethylhexamethylenediamine, pyridine, dimethylaminopyridine, collidine, pyrazine, dimethylpyrazine, quinoline, isoquinoline, quinaldine, benzylmethylimidazole, dimethyl sulfide, diethyl sulfide, diphenyl sulfide , Thiophene, triethylphosphine, triphenylphosphine and triethylarsine. You may use these 1 type or in mixture of 2 or more types. Above all, the use of diethyl ether and THF is recommended.

These Lewis bases are usually added in an amount of about 0.01% by weight to about 50% by weight, preferably about 1% by weight to about 50% by weight, with respect to a solution capable of dissolving an organic metal, and the mixture may be stirred and mixed. Thus, a cleaning liquid composition for excluding organic metals can be obtained. The upper limit of the Lewis base to be added is not particularly limited from the cleaning effect, but if the amount of the remaining organic metal is large, heat is generated due to the heat of coordination with the Lewis base, and therefore it may be determined according to the heat generation amount. .

Hereinafter, an application method of the cleaning liquid composition of the present invention will be described with reference to the drawings, but the application method is merely an example and does not limit the application method of the cleaning liquid composition for removing an organic metal of the present invention. . FIG. 1 shows an example in which a cleaning liquid container and a cleaning liquid recovery container are arranged for the purpose of carrying out the present invention in a generally known organic metal thin film forming apparatus. In the figure, 1
Is an organic metal container, 2 is an organic metal thin film forming apparatus (hereinafter referred to as MO
3 is a cleaning liquid container, 4 is a cleaning liquid recovery container, 5 to 9 are valves, 10 is a vacuum suction device, 11 to 11.
12 indicates a conduit.

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 the generally known method for forming a metal thin film on a substrate using an organic metal. The valve 6 arranged at the inlet is opened, and an inert gas such as hydrogen, argon, or nitrogen is introduced from the valve 9 to pressurize the inside of the organic metal container 1 to pressure-feed the organic metal, or heating or bubbling. Etc. together with the above, the inert gas is accompanied by an organic metal, which is introduced into the thin film forming apparatus 2 via a pipe to form a metal thin film on the substrate in the apparatus. 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 or volatilize and remove the organic metal remaining in the pipe, or to dissolve the organic metal. The inside of the pipe was washed with only the solution to be obtained, for example, hexane or heptane. In the present invention, the cleaning liquid composition is provided with the cleaning liquid container 3 so that the cleaning liquid can be introduced into the pipe connecting the organometallic container 1 and the thin film forming apparatus 2 via the valve 7. A conduit 11 and a conduit 12 are provided above the cleaning liquid container 3, a solution capable of dissolving an organic metal is supplied from the conduit 11 and a Lewis base is supplied from the conduit 12 to the tank 3, and stirring and holding are performed. Has been done. On the other hand, a cleaning liquid recovery container 4 having a vacuum suction device 10 is arranged via a valve 8 in a pipe connecting the organic metal container 1 and the thin film forming apparatus 2. The cleaning method in the apparatus is not particularly limited, but the following procedure can be performed. The valves 5, 6 and 8 are closed and the valve 7 is opened to fill the cleaning liquid into the pipe. The valve 7 is closed, and the valve 8 is opened while vacuum suction is performed by the vacuum suction device 10 provided in the cleaning liquid recovery container 4.
The cleaning liquid in the pipe is collected in the cleaning liquid recovery container 4. Further, the operations of and 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 the vacuum suction device 10 installed in the cleaning liquid recovery container 4 is installed.
It is also possible to collect the organic metal in the pipe in advance in the cleaning liquid container 4 by opening the valve 8 while vacuum suction is performed.
In this case, the heating temperature of the pipe may be a temperature below the decomposition temperature of the organic metal. Further, the cleaning liquid recovery container 4 may be at room temperature, but it is preferable to cool the cleaning liquid recovery container 4 because the cleaning liquid and the like do not escape to the vacuum suction machine side. By carrying out such an operation, not only the vessel wall in the pipe but also the pool portion of the pipe,
Easily cleans organic metal that remains and adheres to the valve gap,
Can be removed.

[0011]

EFFECTS OF THE INVENTION The cleaning composition for removing organic metals of the present invention can be used to remove liquid pools in pipes and valves, which have been difficult to clean in the past.
Since it can be easily washed and removed, it is possible to handle organic metal such as filling the container with organic metal at the time of manufacturing or shipping, and
There is no effect of ignition and smoke when the pipe is disassembled, which is caused by the replacement work of the organic metal container in the OCVD device, and the work can be performed safely.

[0012]

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 Examples and Comparative 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 /
The pressure is increased to cm ² , the valves 5 and 6 are opened, and DMAH is supplied into the MOCVD apparatus 2, and then the valves 5 and 6,
After closing 9 and operating the vacuum suction device 10, the valve 8
Open to open the cleaning liquid recovery container 4 for the DMAH remaining in the pipe.
Recovered. At that time, the cleaning liquid recovery container 4 was cooled to −70 ° C. with hexane / dry ice, and the pipe was heated to 50 ° C. Next, the valve 8 was closed and the valve 7 was opened to fill the pipe with the cleaning liquid. After that, the valve 7 was closed and the valve 8 was opened again to collect the cleaning liquid in the cleaning liquid recovery container 4. After repeating the operation of filling the pipe with the cleaning liquid and the operation of collecting the pipe, the pipes 5 and 6 were removed, but no white smoke was observed in any of the pipes. As the cleaning liquid, heptane containing 5% by weight of THF mixed with stirring was used.

Comparative Example 1 After performing the same cleaning treatment as in Example 1 except that heptane was used as the cleaning liquid, pipes 5 and 6 were removed, and white smoke was generated from both pipes.

[Brief description of the drawings]

FIG. 1 shows an application example of a cleaning liquid composition for removing an organic metal.

[Explanation of symbols]

 1: Organometallic container 2: Organometallic thin film forming device 3: Cleaning liquid container 4: Cleaning liquid recovery container 5: Valve 6: Valve 7: Valve 8: Valve 9: Valve 10: Vacuum suction device 11: Conduit 12: Conduit

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display location C11D 7:32 7:34 7:36)

Claims (8)

[Claims] 1. A cleaning liquid composition for removing an organic metal, comprising a Lewis base in a solution capable of dissolving an organic metal. 2. The cleaning liquid composition for organic metal exclusion 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 indium. Stuff. 3. The cleaning liquid composition for organic metal exclusion according to claim 1, wherein the organic metal is dimethyl aluminum hydride. 4. The cleaning liquid composition for organic metal exclusion according to claim 1, wherein the solution capable of dissolving the organic metal is a hydrocarbon. 5. A solution capable of dissolving an organic metal is hexane,
The cleaning liquid composition for organic metal exclusion according to claim 1, which is at least one of heptane, dodecane, liquid paraffin, benzene, toluene, and xylene. 6. The Lewis base is diethyl ether, dibutyl ether, methylbutyl ether, diphenyl ether, anisole, benzyl ether, dimethoxyethane, diethoxyethane, ethylene glycol dimethyl ether, tetrahydrofuran, dioxane, triethylamine, trioctylamine, dimethylpropylamine, dimethyl. Dodecylamine, dimethylaminotrimethylsilane, dimethylallylamine, diisopropylethylamine, dimethylaniline, benzylethylaniline, tetramethylethylenediamine, tetramethyldiaminopropane, tetramethylhexamethylenediamine,
Pyridine, dimethylaminopyridine, collidine, pyrazine, dimethylpyrazine, quinoline, isoquinoline, quinaldine, benzylmethylimidazole, dimethyl sulfide,
At least one selected from the group consisting of diethyl sulfide, diphenyl sulfide, thiophene, triethylphosphine, triphenylphosphine and triethylarsine.
The cleaning liquid composition according to claim 1, which is a seed. 7. The organometallic-exclusion cleaning liquid composition according to claim 1, wherein the Lewis base is diethyl ether or tetrahydrofuran. 8. The cleaning solution composition for exclusion of organic metals according to claim 1, wherein the content of the Lewis base in the solution capable of dissolving the organic metal is 0.01% by weight to 50% by weight.