JPH08299778A - Solid organometallic compound feeder and its production - Google Patents

Abstract

PURPOSE: To provide a feeder capable of supplying an organometallic compd. solid at ordinary temps. to be fed into an epitaxial growth system in a stabilized concn. for a long time. CONSTITUTION: A stainless steel packing 16 with the porosity controlled to 50-80vol.% is packed in a packing vessel 10 to the 50-80vol.% of the total capacity of the vessel 10, and further an organometallic compd. solid at ordinary temps. is packed as a granular solid 17 to constitute the solid organometallic compd. feeder. When the compd. is produced, the packing 16 is placed in the vessel 10, then the organometallic compd. solid at ordinary temps. is fed, the vessel 10 is heated above the m.p. of the compd. to melt the compd., and the vessel 10 is rotated and cooled.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an apparatus for supplying an organometallic compound which is solid at room temperature and a method for producing the same. More specifically, MO used in manufacturing compound semiconductors
CVD (Metalorganic Chemical
The present invention relates to an apparatus and a method for producing the same, which is useful as a material for epitaxial growth by the Vapor Deposition method or the like and which can supply an organometallic compound which is solid at room temperature at a stable concentration for a long time without waste.

[0002]

2. Description of the Related Art In recent years, III-V and II-VI group compound semiconductors have come to be used in a wide range of fields such as semiconductor light emitting devices and microwave transistors. It has also come to be used in integrated circuits for electronics and integrated circuits for optoelectronics.

Compound semiconductors used for these wide range of applications are MOCs using an organometallic compound as a crystal growth method.
It is manufactured by the VD method. The MOCVD method is one of crystal growth methods often used in forming an epitaxial thin film of a compound or a mixed crystal semiconductor. For example, an organic metal compound such as trimethylindium, trimethylaluminum, and trimethylgallium is used as a raw material, and the heat This is a method of growing a thin film crystal by utilizing a decomposition reaction.

These organometallic compounds used in the MOCVD method are usually filled in a closed container to which gas introduction and discharge pipes are connected, a carrier gas such as hydrogen is introduced into the container, and the organic gas is discharged from the discharge pipe. It is used in the form of obtaining a carrier gas saturated with the vapor of a metal compound.

Generally, an organometallic compound which is solid at room temperature is
It is attached to the inner wall of the container or filled in the form of small particles. However, the solid organometallic compounds filled by these filling methods have a drawback that it is difficult to constantly supply them at a constant concentration by the carrier gas. That is, since it is difficult to keep the contact state between the carrier gas and the solid organometallic compound uniform, the contact area may fluctuate, and it is impossible to supply at a constant concentration.

An intermetallic compound semiconductor formed by epitaxially growing an organometallic compound is significantly adversely affected in electrical and optical characteristics when the composition ratio of the organometallic compound during growth changes. Therefore, in order to obtain a high performance device, it is necessary to stably supply a constant concentration of the organometallic compound. Further, in that case, it is required that the supply device is realized only by the vaporization container without requiring a complicated supply device.

In particular, in the case of a solid organometallic compound such as trimethylindium, when the carrier gas is supplied by the bubbling method in the same container as the liquid organometallic compound, the supply amount varies depending on whether the filling amount of the organometallic compound is large or small. Because of the change, there is a problem that it is difficult to use the filled organometallic compound under constant conditions until the end.

As a method for solving these problems, a method of putting a filling material in a container (Japanese Patent Publication No. 6-20051) and a method of covering the filling material (Japanese Patent Laid-Open No. 1-26551)
No. 1) is known.

[0009]

However, the method of putting the filler in the container has a drawback that the stability is not improved by itself and the concentration is gradually decreased. Also, as for the method of coating the filling, it cannot be used at a stable concentration for a long time, and if the coating is simply performed, the effect cannot be sufficiently obtained when the coating amount of the solid raw material is large, and the filling amount is not sufficient. If it is used many times and used for a long time, the container has to be considerably large, which is uneconomical.

The present invention has been made to solve the above problems, and provides an apparatus capable of supplying a stable concentration of an organometallic compound which is solid at room temperature for a long time and a method of manufacturing the same. With the goal.

[0011]

According to a first aspect of the present invention, a filling material made of stainless steel having a porosity adjusted to 50 to 80% by volume is added to the filling container at a total volume of 50. The solid organometallic compound supply device is characterized in that the organometallic compound is filled so as to be 80% by volume, and further, the organometallic compound which is solid at room temperature is filled as a granular solid.

Further, in the invention according to claim 2 of the present invention, in the apparatus according to claim 1, more than 100 parts by weight of the organometallic compound which is solid at room temperature is filled with respect to 100 parts by weight of the stainless filler. Is characterized by.

Further, the invention according to claim 3 of the present invention is
The apparatus according to claim 1, wherein the organometallic compound which is solid at room temperature is trimethylindium.

Next, in the invention according to claim 4 of the present invention, a stainless filler having a porosity adjusted to 50 to 80% by volume is filled in the filling container in an amount of 50 to 80 with respect to the total volume of the filling container.
After filling so as to be volume%, add an organometallic compound that is solid at room temperature, heat the filling container to a temperature above the melting point of the organometallic compound, melt the organometallic compound in the filling container, and then rotate the container. The method for producing a solid metal compound supply device is characterized in that the organometallic compound is filled in the filling container as a granular solid by cooling while allowing it to proceed.

According to a fifth aspect of the present invention, in the manufacturing method according to the fourth aspect, 10 parts by weight of the organometallic compound solid at room temperature is added to 100 parts by weight of the stainless filler.
It is characterized by filling more than 0 parts by weight.

The invention according to claim 6 of the present invention is characterized in that, in the manufacturing method according to claim 4, the organometallic compound which is solid at room temperature is trimethylindium.

Further, the invention according to claim 7 of the present invention is
The manufacturing method according to claim 4, wherein the number of rotations of the container during cooling while rotating the filling container is 50 to 100 rpm.
Is characterized in that.

Next, the present invention will be described in more detail. FIG. 1 shows an example of the solid organometallic compound supply device of the present invention. The filling container 10 is provided with a nozzle 11, a nozzle 13 having a valve 12, and a nozzle 15 having a valve 14. The filling container 10 is filled with a stainless filler 16 having a porosity (porosity) adjusted to 50 to 80% by volume so as to be 50 to 80% by volume with respect to the total volume of the container, and further solid at room temperature. The granular organometallic compound 17 which is a granular solid of the organometallic compound is filled.

The filler 16 made of stainless steel is obtained by rolling a wire mesh of about 100 mesh into small pieces and cutting them into 3 mmφ × 3 mmL, and further in the radial direction so that the porosity (porosity) becomes 50 to 80% by volume. It is obtained by applying a load and adjusting by crushing. Porosity (porosity) is 50
If it is less than%, the organometallic compound cannot be sufficiently retained, which is uneconomical. Further, when the content is 80% by volume or more, it is difficult to adhere when the filling container 10 containing the organometallic compound is rotated and granulated, so that the effect of sufficiently dispersing the organometallic compound in the filling container is small and a stable concentration is obtained. Supply becomes difficult.

The stainless filling 16 is filled so as to be 50 to 80% of the total volume in the filling container. Fifty
% Or less, it is uneconomical because the filling amount of the organometallic compound decreases accordingly. When it is 80% or more, the amount of movement of the stainless steel filler 16 is small when the filling container 10 containing the organometallic compound is rotated and granulated, so that the granulated organometallic compound having a desired function is obtained. I can't.

Examples of the organometallic compound which is solid at room temperature include trimethylindium. 100 parts by weight of the organometallic compound is 100 parts by weight of the stainless steel filler.
It is desirable to fill more than parts by weight. If the amount is 100 parts by weight or less, the desired function cannot be obtained, and it becomes impossible to supply a stable concentration for a long time. Further, the filling amount of the organometallic compound that can be filled with respect to the capacity of the filling container 10 becomes small, which is uneconomical and not preferable.

Next, an example of a method for manufacturing this solid organometallic compound supply device will be described. First, the nozzle 11 of the well-washed filling container 10 is opened, and the stainless filler 16 is put therein. After closing the nozzle 11, the inside is replaced with an inert gas. After reducing the pressure to preferably 10 torr or less, an inert gas is introduced. The operation is repeated 2-3 times so that impurities such as oxygen do not remain in the system.

Next, the organometallic compound is placed in the filling container 10. In this case, the nozzle 11 may be filled in an inert gas, but preferably, the nozzle 13 is connected to another container (not shown) containing an organometallic compound, and the connecting portion is sufficiently filled. After the replacement, the valve 12 is opened and sublimation is used to fill a predetermined amount. At that time, when the filling amount of the organometallic compound is 100 parts by weight or less with respect to 100 parts by weight of the stainless steel filler, a desired function cannot be obtained when the filling container 10 is rotated to granulate the organometallic compound. Therefore, it is not preferable.

Then, the filling container 10 is heated to a temperature above the melting point of the organometallic compound. The heating method is not particularly limited, and heating may be performed using an oil bath, a constant temperature bath or the like. For example, when the organic metal compound is trimethylindium, the temperature may be about 90 to 110 ° C., which is higher than the melting point.

After the predetermined temperature is reached, the filling container 10 is filled with the granular organometallic compound 17 in which the organometallic compound is solidified by cooling the filling container 10 while rotating. The rotation of the filling container 10 is performed by fixing the filling container 10 in a cylindrical container (not shown) using a pot mill rotating table or the like,
The filling container 10 is cooled while rotating the cylindrical container on the rotary table as it is. The rotation speed at that time is 50 to 100 r
pm is preferred. At 50 rpm or less or 100 rpm or more, the organometallic compound is unevenly distributed in the vicinity of the outer peripheral portion inside the filling container 10, and thus desired characteristics cannot be obtained, which is not preferable. The filling container 10 may be forcibly cooled, but it is sufficient to naturally cool it while rotating it.

[0026]

In the solid organometallic supply device configured as described above, since the organometallic compound is sufficiently dispersed and filled in the filling container as a granular solid, the organometallic compound which is solid at room temperature and is useful as a material for epitaxial growth. The compound can be supplied at a stable concentration for a long time without waste.

[0027]

EXAMPLES Hereinafter, examples of the solid organometallic compound supply device according to the present invention will be described in detail.

Example 1 A 100-mesh stainless wire mesh was cut into a piece of 3 mm × 15 mm and then rolled into a diameter of about 3 mmφ. 100 g of a material crushed in the radial direction so that the porosity is about 70% by volume is prepared, and the stainless filler 16 is prepared. The volume at this time was about 150 ml.

As shown in FIG. 1, an outer diameter of 60.5 mmφ,
Filling container 1 with a body height of 115 mmL and an internal volume of 200 ml
0 was thoroughly washed with water and dried, then the nozzle 11 was opened, 100 g of the above-mentioned stainless steel filler 16 was charged, the nozzle 11 was closed, and then a vacuum pump was connected to the nozzle 13.
A vacuum was drawn up to 0.1 torr. Then nozzle 1
Helium gas was introduced from 5 to perform gas replacement. After repeating this operation three times, the nozzle 13 was connected to a container (not shown) containing trimethylindium, and the valve 1
2 was opened, and sublimation was used to transfer and fill the filling container 10. The filling amount was 110 g.

After that, the filling container 10 was immersed in an oil bath, heated to 100 ° C. and held for 0.5 hr, and then the filling container 10 was taken out and fixed in a cylindrical container (not shown). This was placed on a pot mill rotary table (not shown), and the filling container 10 was rotated at 60 rpm for 3 hours. afterwards,
The filling container 10 was taken out. Thus, the solid organometallic compound supply device was manufactured.

Next, it was tested whether or not the organometallic compound could be stably supplied by this apparatus. That is, the filling container 10 containing the trimethylindium is installed in a thermostat (not shown), and high-purity helium is passed from the nozzle 13 into the filling container 10 to gasify the trimethylindium. The phases were measured with a gas densitometer (manufactured by Aprioli, not shown). FIG. 2 shows the relationship between the feed amount (ratio to the total filling amount of trimethylindium) and the concentration of trimethylindium. As shown in FIG. 2, it was confirmed that the apparatus of the present example can stably supply the concentration for a long time, and it was confirmed that the apparatus has excellent stability.

Example 2 Example 2 was prepared in the same manner as in Example 1 except that the amount of the organometallic compound used in Example 1 was 120 g based on 100 g of the stainless steel filler. When tested in the same manner as in Example 1, as in Example 1, the concentration can be stably supplied for a long time,
It was confirmed that the stability was excellent.

Example 3 The procedure of Example 1 was repeated, except that the amount of the organometallic compound used in Example 1 was 130 g relative to 100 g of the stainless steel filler. When tested in the same manner as in Example 1, as in Example 1, the concentration can be stably supplied for a long time,
It was confirmed that the stability was excellent.

Comparative Example 1 The organometallic compound in Example 1 was prepared in the same manner as in Example 1 except that heating, melting and rotation treatment were not performed. When tested in the same manner as in Example 1, as shown in FIG. 2, it was continuously used for a long time.

Comparative Example 2 Example 1 except that the filling amount of the organometallic compound in Example 1 was 50 g per 100 g of the stainless steel filling.
Prepared as in. When tested in the same manner as in Example 1,
The result was very similar to that of Comparative Example 1, and it could be used for a long time.

Comparative Example 3 Example 3 was replaced with a commercially available Dickson packing (porosity about 94% by volume) in place of the stainless steel filler adjusted to have a porosity of about 70% by volume in Example 1. Prepared as in 1. When tested in the same manner as in Example 1, it lacked stability as shown in FIG. 2 and could not be used for a long time.

Comparative Example 4 Preparation was performed in the same manner as in Example 1 except that the cylindrical container in Example 1 was rotated at 150 rpm for 3 hours. When tested in the same manner as in Example 1, the results were very similar to those in Comparative Example 3, lacking in stability, and could not be used for a long time.

Comparative Example 5 The procedure of Example 1 was repeated, except that the amount of the organometallic compound used in Example 1 was 100 g based on 100 g of the stainless steel filler. When tested in the same manner as in Example 1, the results were very similar to those in Comparative Example 3, lacking in stability, and could not be used for a long time.

[0039]

As is apparent from the above description, according to the present invention, the organometallic compound can be sufficiently dispersed and filled in the filling container as a granular solid, and the carrier gas and the solid organometallic compound can be filled. The contact state with the compound can be kept uniform. Therefore, it is possible to supply the organometallic compound, which is useful as a material for epitaxial growth, and which is solid at room temperature at a stable concentration for a long time without waste and without unnecessarily increasing the size of the filling container itself.

[Brief description of drawings]

FIG. 1 is a sectional view showing an example of a solid organometallic compound supply device of the present invention.

FIG. 2 is a graph showing changes in the concentration of an organometallic compound gasified and supplied from a solid organometallic compound supply device.

[Explanation of symbols]

 10 Filling Container 11 Nozzle 12 Valve 13 Nozzle 14 Valve 15 Nozzle 16 Stainless Steel Filling Material 17 Granular Organometallic Compound

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical indication C30B 35/00 7202-4G C30B 35/00 H01L 21/205 H01L 21/205 (72) Inventor Kaneko Achievement 28, Nishi-Fukushima, Kubiki-mura, Nakakubiki-gun, Niigata Prefecture Shin-Etsu Chemical Co., Ltd. Synthetic Technology Laboratory (72) Inventor Kohei Sato 1-28, Nishi-Fukushima, Kubiki-mura, Nakakubiki-gun, Niigata Prefecture 1 Shin-Etsu Chemical Co., Ltd. Company Synthetic Technology Laboratory

Claims (7)

[Claims] 1. A filling container is filled with a stainless filler having a porosity adjusted to 50 to 80% by volume so as to be 50 to 80% by volume with respect to the total volume of the filling container, and further solid at room temperature. A solid organometallic compound supply device, characterized in that the organometallic compound of (1) is filled as a granular solid. 2. The solid organometallic compound supply device according to claim 1, wherein the organometallic compound which is solid at room temperature is filled in an amount of more than 100 parts by weight based on 100 parts by weight of the stainless steel filler. 3. The solid organometallic compound supply device according to claim 1, wherein the organometallic compound which is solid at room temperature is trimethylindium. 4. A filling container is filled with a stainless filler having a porosity adjusted to 50 to 80% by volume so as to be 50 to 80% by volume with respect to the total volume of the filling container, and then solid at room temperature. Of the organometallic compound, and heating the filling container above the melting point of the organometallic compound to melt the organometallic compound in the filling container, and then cooling while rotating the filling container, A method for manufacturing a solid metal compound supply device, which comprises filling the organometallic compound as a granular solid. 5. The method for producing a solid organometallic compound supply device according to claim 4, wherein the organometallic compound which is solid at room temperature is filled in an amount of more than 100 parts by weight with respect to 100 parts by weight of the stainless steel filler. 6. The method for manufacturing a solid organometallic compound supply device according to claim 4, wherein the organometallic compound which is solid at room temperature is trimethylindium. 7. The method for producing a solid organometallic compound supply device according to claim 4, wherein the number of rotations of the container when cooling the filling container while cooling is 50 to 100 rpm.