KR101358204B1 - Method and container for filling solid organometallic compound - Google Patents

Abstract

The present invention provides a solid organometallic compound to a filling container for a solid organometallic compound which enables a solid organometallic compound to be stably supplied to a device for vapor phase epitaxial growth such as a MOCVD apparatus at a constant concentration for a long time. It is an object to provide a method for filling a compound.
The present invention is a method for filling a solid organic metal compound into a filling container for a solid organic metal compound, wherein the solid organic metal compound is a particle having a particle diameter of 8 mm or less, and a particle having a particle diameter of 2.5 to 6 mm is a solid organic metal compound. It is related with the filling method of the solid organometallic compound to the filling container for solid organometallic compounds, Comprising: it is essential to include in the inside.

Description

Method and container for filling solid organometallic compound

The present invention relates to a filling method of a solid organometallic compound into a filling container and a filling container of a solid organometallic compound filled by the filling method. More specifically, the material for vapor phase epitaxial growth by the Metalorganic Chemical Vapor Deposition (hereinafter abbreviated as "MOCVD") method used when manufacturing materials for electronic industry, such as a compound semiconductor. A filling container in which a solid organometallic compound is filled with a method for filling a solid organometallic compound into a filling container that enables a phosphorus solid organometallic compound to be stably supplied to a device for vapor phase epitaxial growth at a constant concentration for a long time, and the filling method It is about.

Organometallic compounds, such as trimethyl indium, are used widely as a raw material at the time of manufacturing an electronic industry material.

As a manufacturing method of the electronic industry material using an organometallic compound, gas phase epitaxial growth by MOCVD method etc. is used a lot recently. For example, a thin film of a compound semiconductor is produced by MOCVD, and at that time, organic metal compounds such as trimethylaluminum, trimethylgallium, and trimethylindium are used as raw materials.

When using these organometallic compounds in the MOCVD method, when the organometallic compound is solid under the conditions under which the organometallic compound is used, the carrier gas inlet port 2a and the carrier gas outlet port 3a as shown in FIG. Is filled into a filling container (hereinafter referred to as filling container A), a carrier gas such as hydrogen gas is introduced into the container from the carrier gas inlet 2a, and an organometallic compound is introduced from the carrier gas outlet 3a. A method of discharging as saturated gas in the carrier gas and supplying it to the MOCVD apparatus is used.

In that case, when this organometallic compound is solid at the temperature used in said supply, the flow path which a carrier gas passes through in solid container metal A without sufficient contact with a solid organometallic compound in the filling container A. Is difficult to maintain a uniform contact state between the carrier gas and the solid organometallic compound, and it is difficult to stably supply the solid organometallic compound from the filling container A to the MOCVD apparatus stably at a constant concentration for a long time by the carrier gas. There is a problem. In addition, in the supply of the solid organometallic compound by the method using the carrier gas as described above, if the amount of the solid organometallic compound to be filled in the filling container A is increased, the solid organometallic compound can be stably supplied to the MOCVD apparatus. The proportion of the amount decreases with respect to the amount of the solid organometallic compound charged, and as a result, there is a problem that the amount of the remaining organometallic compound in the filling container increases, so that the solid organometallic compound cannot be effectively used.

In order to solve these problems, various proposals are made | formed about the method at the time of filling solid container metal A to filling container A. For example, Japanese Patent Application Laid-open No. Hei 5-39915, Japanese Patent Application Laid-open No. Hei 6-20051, Japanese Patent Application Laid-open No. Hei 7-58023, Japanese Patent Application Laid-open No. Hei 8-250440 In Japanese Patent Laid-Open No. 8-299778 and the like, a method of filling a filling container with a filler with a solid organometallic compound has been proposed. For example, Japanese Patent No. 261530 and the like propose a method of filling a filling container A with a solid organometallic compound coated on an inert carrier.

In addition, in the method of solving the above-mentioned problem, various proposals are made regarding the structure of the filling container itself which fills a solid organometallic compound. For example, in Japanese Patent Application Laid-Open No. 2-124796, as shown in Fig. 34, a diffuser 20a is formed in the carrier gas inlet for homogenizing the gas, and the carrier is provided with respect to the solid organic metal compound. A filling container (hereinafter referred to as filling container B) having a structure in which gas is uniformly distributed has been proposed.

For example, in JP-A-10-223540, a filling container (hereinafter referred to as filling container C) having a solid organometallic compound placement chamber 21a having air permeability as shown in FIG. Proposed.

For example, Japanese Patent Laid-Open No. 2002-83777 discloses a filling container (hereinafter referred to as filling container D) in which a porous inlet chamber as shown in FIG. 36 is used as a filling portion of a solid organometallic compound. have.

On the other hand, Japanese Patent Laid-Open No. 2003-160865 discloses a method of controlling the particle diameter when a ruthenium compound is used for stabilizing the supply of a solid organometallic compound.

However, Japanese Patent Application Laid-open No. Hei 5-39915, Japanese Patent Publication No. Hei 6-20051, Japanese Patent Application Laid-Open No. 7-58023, Japanese Patent Application Laid-open No. Hei 8-250440, and Japanese Patent Publication Filling in Japanese Patent Application Laid-Open No. 8-299778, Japanese Patent No. 261530, Japanese Patent Publication No. 2-124796, Japanese Patent Publication No. 10-223540, and Japanese Patent Publication No. 2002-83777 In the proposal of a method and a filling container, the examination of the particle diameter of the solid organometallic compound itself to fill a filling container is not made | formed.

In addition, about the influence on rubbing supply of the ruthenium compound in the particle diameter control of Unexamined-Japanese-Patent No. 2003-160865, etc., the effect of the initial stage of supply is described by examination of several film formings. It is not clear about the effects of stable supply of ruthenium compounds at a constant concentration for a long time. As a result of the present inventor's examination, in supplying the solid organometallic compound using a carrier gas, it discovered that the particle diameter control method for obtaining not only initial stability but long-term stability exists.

SUMMARY OF THE INVENTION The present invention solves the above problems, and the problem to be solved by the present invention is to provide a solid organometallic compound which can be stably supplied to a device for vapor phase epitaxial growth such as a MOCVD apparatus at a constant concentration for a long time. It is to provide a filling container in which a solid organometallic compound is filled by a method for filling a solid organometallic compound into a filling container for a compound, and a filling method thereof.

In order to solve the above-mentioned problems, the inventors have investigated, in order to supply a solid organometallic compound at a constant concentration for a long time by filling a solid organometallic compound in a filling container and circulating a carrier gas, When filling the filling container for an organometallic compound, by controlling the particle diameter of the solid organometallic compound to a particle diameter of a specific size or less, not only the initial supply stability but also the supply stability can be maintained for a long time. The present invention was completed and the present invention was completed.

That is, when filling a solid organometallic compound into the filling container for solid organometallic compounds, the particle | grains of a solid organometallic compound whose particle diameter is 8 mm or less and particle diameters 2.5-6 mm are essential in a solid organometallic compound. It relates to a method for filling a solid organometallic compound into a filling container for a solid organometallic compound, characterized in that it is included.

Moreover, in the filling method of this invention, a filler can coexist and use together with the solid organometallic compound which controlled the particle diameter as mentioned above.

That is, in the method for filling a solid organometallic compound into a filling container for a solid organometallic compound, the solid organometallic compound is a particle having a particle diameter of 8 mm or less, and particles having a particle diameter of 2.5 to 6 mm are solid organometallic compounds. It is related with the filling method of the solid organometallic compound to the filling container for solid organometallic compounds, Comprising: it is essential to include in the inside.

Moreover, in the filling method of the solid organometallic compound in the filling container for solid organometallic compounds of this invention, a filler is filled with a solid organometallic compound, and the thing of the said filler is 0.8-8 mm in size.

Moreover, in the filling method of the solid organometallic compound in the filling container for solid organometallic compounds of this invention, the said filling container for solid organometallic compounds is carried out to the filling container for solid organometallic compounds which has a carrier gas introduction port and a carrier gas discharge port. Wherein the inside of the filling container is divided into a plurality of vertical spaces, and the carrier gas introduced from the carrier gas inlet flows through each of the vertical spaces and is discharged from the carrier gas discharge port. It is a filling container for metal compounds, It is characterized by the above-mentioned.

Moreover, in the filling method for a solid organometallic compound in the filling container for solid organometallic compounds of this invention, the solvent of (a)-(c) can be provided in the said filling container for solid organometallic compounds.

(a) the interior of the filling container is partitioned longitudinally into at least one or more partitions so that the interior of the filling container is partitioned into at least two spaces;

(b) a space inside the filling container formed by partitioning the partition wall, the space having a carrier gas inlet and a space having a carrier gas outlet;

(c) The partition wall inside the filling container has a partition having an opening for flowing carrier gas from the carrier gas inlet to the carrier gas outlet through each space in the filling container.

In the filling method of the solid organometallic compound in the filling container for solid organometallic compounds of the present invention, in the filling container for the solid organometallic compound, the solvent of (a) to (c) is provided in the opening portion. In the case of arranging the opening part in the lower part of the partition wall, when the opening part is 1/3 or less of the container inner height from the inner bottom surface of a filling container, and an opening part is arrange | positioned in the upper part of a partition wall, the container inner height from the inner bottom surface of a filling container. It is characterized in that the openings are provided at positions 2/3 or more of each.

Moreover, in the filling method of the solid organometallic compound to the filling container for solid organometallic compounds of this invention, in the said packing container for solid organometallic compounds, it is equipped with the solvent of (a)-(c), and it is a partition It is characterized by having a filling port for filling the solid organometallic compound in the space inside the filling container formed by partitioning.

Moreover, in the filling method of the solid organometallic compound in the filling container for solid organometallic compounds of this invention, in the filling container for solid organometallic compounds, the filling container for solid organometallic compounds has a carrier gas introduction port and a carrier gas discharge port. The inside of the filling container is divided into a plurality of vertical spaces, and the carrier gas introduced from the carrier gas inlet is distributed by the carrier gas flow direction reversal means through each of the vertical spaces in a downward flow, and is separated from the carrier gas outlet. It is characterized by a filling container for solid organometallic compounds having a discharged structure.

Moreover, in the filling method for a solid organometallic compound in the filling container for solid organometallic compounds of this invention, the solvent of (d)-(h) can be provided in the said filling container for solid organometallic compounds.

(d) the interior of the filling container is partitioned longitudinally into at least one or more partitions so that the interior of the filling container is partitioned into at least two spaces;

(e) a space inside the filling container formed by partitioning with a partition wall, the space including a carrier gas inlet and a space including a carrier gas outlet;

(f) Partition walls inside the filling container, the partition wall having a communication channel having a lower opening and an upper opening for circulating the carrier gas from the carrier gas inlet to the carrier gas outlet through each space in the filling container. ;

(g) a contact flow path, wherein the carrier gas introduced into the filling container is introduced from the lower opening of the communication flow path and discharged into the upper opening;

(h) A filling container for a solid organometallic compound having a discharge passage having a lower opening for discharging a carrier gas from a lower portion of a space having a carrier gas discharge port to a carrier gas discharge port.

Moreover, in the filling method of the solid organometallic compound to the filling container for solid organometallic compounds of this invention, in the said packing container for solid organometallic compounds, what is provided with the solvent of (d)-(h) is said In the communication flow path, the lower opening of the communication flow path is located at 1/3 or less of the height of the inside of the container from the inner bottom surface of the filling container, and the upper opening of the communication flow path is at least 2/3 of the height inside the container from the inner bottom surface of the filling container. And a lower opening of the discharge passage in the discharge passage is provided at a position equal to or less than 1/3 of the inside height of the container from the inner bottom surface of the filling container.

Moreover, in the filling method of the solid organometallic compound to the filling container for solid organometallic compounds of this invention, in the said packing container for solid organometallic compounds, it is equipped with the solvent of (d)-(h), It is characterized by having a filling port for filling the solid organometallic compound in the space inside the filling container formed by partitioning.

Moreover, in the filling method of the solid organometallic compound in the filling container for solid organometallic compounds of this invention, when it is equipped with the solvent of (d)-(h) in the said filling container for solid organometallic compounds, it is a partition. It is characterized by having a filling port for filling the solid organometallic compound in the space inside the filling container formed by partitioning.

In the filling method of the solid organometallic compound in the filling container for solid organometallic compounds of the present invention, trimethylindium can be used as the solid organometallic compound.

Moreover, this invention relates to the filling container for solid organometallic compounds which filled the solid organometallic compound by said filling method of this invention.

ADVANTAGE OF THE INVENTION According to this invention, when filling a solid organometallic compound in the filling container for solid organometallic compounds, initial stability can be ensured because the particle diameter of a solid organometallic compound contains the particle | grains of a specific size essentially. In addition, a solid organometallic compound can be supplied to a device for vapor phase epitaxial growth such as a MOCVD device stably for a long time.

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic diagram which shows one Embodiment of the filling container of this invention, FIG. 1A is sectional drawing, FIG. 1B is a top view, and FIG. 1C is a perspective view.
FIG. 2: is a schematic diagram which shows one Embodiment of the filling container of this invention, FIG. 2A is sectional drawing, FIG. 2B is top view.
FIG. 3 is a schematic view showing one embodiment of the filling container of the present invention, FIG. 3A is a sectional view, and FIG. 3B is a plan view.
Fig. 4 is a schematic view showing one embodiment of the filling container of the present invention, Fig. 4A is a sectional view and Fig. 4B is a plan view.
FIG. 5: is a schematic diagram which shows one Embodiment of the filling container of this invention, FIG. 5A is a perspective view, FIG. 5B is sectional drawing.
FIG. 6: is a schematic diagram which shows one Embodiment of the filling container of this invention, FIG. 6A is a perspective view, FIG. 6B is sectional drawing.
FIG. 7: is a schematic diagram which shows one Embodiment of the filling container of this invention, FIG. 7A is sectional drawing, FIG. 7B is top view, and FIG. 7C is a perspective view.
FIG. 8: is a schematic diagram which shows one Embodiment of the filling container of this invention, FIG. 8A is sectional drawing, FIG. 8B is top view, and FIG. 8C is a perspective view.
It is a schematic diagram which shows one Embodiment of the filling container of this invention, FIG. 9A is a perspective view, FIG. 9B is sectional drawing.
It is a schematic diagram which shows one Embodiment of the filling container of this invention, FIG. 10A is a perspective view, FIG. 10B is sectional drawing.
It is a schematic diagram which shows one Embodiment of the filling container of this invention, FIG. 11A is a perspective view, FIG. 11B is sectional drawing.
It is a schematic diagram which shows one Embodiment of the filling container of this invention, FIG. 12A is sectional drawing, FIG. 12B is a top view, and FIG. 12C is a perspective view.
It is a schematic diagram which shows one Embodiment of the filling container of this invention, FIG. 13A is sectional drawing, FIG. 13B is a top view, and FIG. 13C is a perspective view.
It is a schematic diagram which shows one Embodiment of the filling container of this invention, FIG. 14A is sectional drawing, and FIG. 14B is a top view.
FIG. 15: is a schematic diagram which shows one Embodiment of the filling container of this invention, FIG. 15A is sectional drawing, FIG. 15B is top view.
It is a schematic diagram which shows one Embodiment of the filling container of this invention, FIG. 16A is sectional drawing, and FIG. 16B is a top view.
It is a perspective view which shows one Embodiment of the filling container of this invention.
It is a perspective view which shows one Embodiment of the filling container of this invention.
It is a perspective view which shows one Embodiment of the filling container of this invention.
20 is a perspective view showing one embodiment of the filling container of the present invention.
It is a schematic diagram which shows one Embodiment of the filling container of this invention, FIG. 21A is a perspective view, FIG. 21B is sectional drawing.
It is a schematic diagram which shows one Embodiment of the filling container of this invention, FIG. 22A is a perspective view, FIG. 22B is sectional drawing.
It is a schematic diagram which shows one Embodiment of the filling container of this invention, FIG. 23A is a perspective view, FIG. 23B is sectional drawing.
24 is a schematic view showing one embodiment of the filling container of the present invention, FIG. 24A is a perspective view, and FIG. 24B is a sectional view.
FIG. 25 is a schematic view showing one embodiment of the filling container of the present invention, FIG. 25A is a perspective view, and FIG. 25B is a sectional view.
It is a schematic diagram which shows one Embodiment of the filling container of this invention, FIG. 26A is a perspective view, FIG. 26B is sectional drawing.
It is a schematic diagram which shows one Embodiment of the filling container of this invention, FIG. 27A is a perspective view, FIG. 27B is sectional drawing.
FIG. 28: is a schematic diagram which shows the filling container used in Example 1, FIG. 28A is sectional drawing, FIG. 28B is a top view, and FIG. 28C is a perspective view.
Fig. 29 is a graph showing the test result of the supply stability of trimethyl indium in the first example (relationship between the use ratio of trimethyl indium supplied and the supply amount of trimethyl indium per hour).
It is a figure which shows the test result (the relationship between the use ratio of trimethyl indium supplied and the supply amount of trimethyl indium per hour) of the trimethyl indium supply stability in the comparative example 1. FIG.
FIG. 31 shows the test results of the supply stability of trimethyl indium in Example 2 (relationship between the use ratio of trimethyl indium supplied and the supply amount of trimethyl indium per hour).
It is a figure which shows the test result of the supply stability of trimethyl indium in the comparative example 2 (relationship between the use ratio of trimethyl indium supplied and the supply amount of trimethyl indium per hour).
FIG. 33: is a schematic cross section which shows the conventional filling container A. FIG.
It is a schematic cross section which shows the conventional filling container B. FIG.
It is a schematic cross section which shows the conventional filling container C.
36: is a schematic cross section which shows the conventional filling container D. FIG.

Hereinafter, the filling method of the present invention and a filling container filled with the solid organometallic compound by the filling method will be described in more detail.

In the filling method of the present invention, when the solid organometallic compound is filled into a filling container for a solid organometallic compound, the particle diameter of the solid organometallic compound is 8 mm or less, and the particle diameter is 2.5 to 6 mm. It is characterized in that it is essentially included in the solid organometallic compound.

In the present invention, as the size of the particles of the solid organometallic compound, for example, in the case of filling the filling container with a solid, it can be made to pass through the size of the opening of the filling opening provided in the filling container, 8 mm or less, preferably 6 mm or less, more preferably 5 mm or less can be used, and the particle | grains whose particle diameter is 2.5-6 mm shall be essentially included in a solid organometallic compound.

When the solid organometallic compound exceeds 8 mm, when the carrier gas flow rate is increased, the contact area where the carrier gas is in contact with the solid organometallic compound is reduced, so that sufficient time for reaching the saturation state cannot be obtained. Therefore, long-term supply stability cannot be obtained.

The proportion of 2.5 to 6 mm particles per solid organometallic compound can be, for example, 30 to 100%, preferably 40 to 100%, and more preferably 50 to 100%.

As a reason for this, if the abundance ratio of 2.5-6 mm particles per solid organometallic compound is small, for example, when many particle | grains larger than 6 mm are included, with carrier gas flow volume increase as mentioned above, It is conceivable that sufficient contact between the carrier gas and the solid organometallic compound particles is not obtained, and long-term supply stability is not obtained. For example, in the case of containing a lot of particles smaller than 2.5 mm, the carrier Since the contact area between the gas and the particles is large, the initial supply stability can be satisfactorily obtained, but during long-term use, as the solid organometallic compound is supplied to the carrier gas as saturated vapor and consumed, the particles become finer, It is difficult for the carrier gas to pass between fine particles, and the carrier gas passes between larger particles, that is, a solid Group metal compound and the carrier gas is a phenomenon which is likely to discard flow path is formed to pass through while not obtained sufficient contact occurs, it is considered that the result is not obtained In the supply stability in long-term use.

It does not specifically limit as a method of shape | molding the particle | grain of this solid organometallic compound, The shaping | molding method known so far can be used as it is. As an example of this shaping | molding method, the method of grind | pulverizing the lump of a solid organometallic compound, for example, the method of liquefying a solid organometallic compound and solidifying this, etc. can be used.

Moreover, the control method of the particle diameter of a solid organometallic compound is not specifically limited, either, The method of preparing the particle diameter known so far can be used as it is. As the method for controlling the particle diameter, for example, in the method of pulverizing the lump of the solid organometallic compound, after the pulverization of the solid organometallic compound, a method of recovering what has passed through a sieve having a constant size through a sieve; For example, in the method of liquefying a solid organometallic compound and solidifying it, the method of controlling the weight of droplets, the method of controlling the shape of a liquid to the size of a template using a template, etc. are illustrated. Can be.

In the above-described method, the method for obtaining a particle diameter of the solid organometallic compound having a particle diameter of 8 mm or less and having a particle diameter of 2.5 to 6 mm essentially included in the solid organometallic compound is particularly limited. Although not specifically, for example, an appropriately ground solid organic metal compound is sieved without passing through a sieve having a sieve hole of 8 mm in size, and sieved solid organic metal of 8 mm or less. Particles of the compound are also pulverized appropriately to separate particles which pass through a sieve having a 6 mm sieve and do not pass through a 2.5 mm sieve, so as to have a solid organic particle size of 2.5 to 6 mm. After obtaining a metal compound, this particle diameter is obtained by making the particle | grains of 2.5-6 mm into an essential component of a solid organometallic compound, and passing through the sieve which has a sieve hole of the size of 8 mm. A method of mixing a solid organometallic compound having a diameter of 8 mm or less, or a solid organometallic compound appropriately pulverized so as to include particles having a particle diameter of 2.5 to 6 mm, or a body hole having a size of 2.5 to 6 mm It is possible to use a method for recovering the whole amount of the product that has passed through the sieve having

Thus, in the method of filling a solid organometallic compound into a filling container, and circulating a carrier gas, the particle | grains whose particle diameter of a solid organometallic compound are 8 mm or less and whose particle diameters are 2.5-6 mm are solid organometallic. The reason for obtaining the effect of supplying a solid organometallic compound at a constant concentration for a long period of time by essentially including it in the compound is to include a particle having a particle diameter of 2.5 to 6 mm, thereby providing a space formed from particles of that size. In this case, it is considered that the carrier gas becomes easy to flow, and in the case where the particle diameter of the solid organometallic compound does not include particles having 2.5 to 6 mm, the solid organometallic compound is supplied in the space formed from the particles. In the initial stage, the carrier gas is a solid organic gold in the solid organometallic compound. Although sufficient contact with the compound is obtained, it is considered that a flow path through which the carrier gas passes without sufficient contact with the solid organometallic compound is easily formed in the course of long-term use.

Therefore, in the supply of the solid organometallic compound using the carrier gas, if the particle diameter of the solid organometallic compound does not include particles having a particle diameter of 2.5 to 6 mm, there is no problem in the initial supply stability. Problem arises. As in the present invention, by using particles having a particle diameter of 2.5 to 6 mm, which are essential in the solid organometallic compound, the flow path is less likely to be formed, the supply amount is stabilized in the short term, and the long term It is thought that carrier gas can distribute | circulate stably in the packed layer of a solid organometallic compound, and supply stability of a solid organometallic compound improves.

In the filling method of the present invention, the structure of the filling container for a solid organometallic compound that can be used is not particularly limited, and for example, a container as is known so far can be used as it is.

In the filling method of the present invention, in addition to the filling container for the solid organometallic compound having the above structure, in the filling container for the solid organometallic compound having a carrier gas inlet and a carrier gas outlet, the inside of the filling container is divided into a plurality of vertical spaces. A filling container for a solid organometallic compound, which is fractionated and has a structure in which the carrier gas introduced from the carrier gas inlet flows through each vertical space and is discharged from the carrier gas outlet.

An example of the filling container for solid organometallic compounds is shown in FIGS. As shown in FIGS. 1-4, the filling container for solid organometallic compounds used by the filling method of this invention partitions the inside of a filling container in the longitudinal direction by the at least 1 or more partition wall 1, and is at least 2 or more It has a structure partitioned into spaces. The partition system of the space by the partition 1 may have a structure in which the space is partitioned, for example, as shown in FIGS. 1 to 4.

The outer shape of the filling container may be, for example, a container having a columnar shape such as a triangular column, a square column, a pentagonal column, a hexagonal column, or the like, in addition to the cylindrical container as shown in FIGS. 1 to 4.

In addition, the filling container for a solid organometallic compound used in the filling method of the present invention has a carrier gas inlet (2) through one space inside the filling container formed by partitioning with the partition wall (1), and in one of the remaining spaces. As a structure which has the carrier gas discharge port 3 which communicates, the thing of the structure of FIGS. 1-4 is mentioned, for example. The carrier gas is introduced from the carrier gas inlet 2 into the filling container filled with the solid organometallic compound, and the inside of the filling container is passed through, and the organic metal compound is discharged from the carrier gas outlet 3 as a gas saturated in the carrier gas. To the MOCVD apparatus. The mounting position of the carrier gas inlet 2 and the carrier gas outlet 3 to the filling container is determined by, for example, the partitioning method of the space by the partition wall 1, the type of use of the filling container, or the like. There exists a structure which has the carrier gas introduction port 2 and the carrier gas discharge port 3 in the upper part, and also has a structure which has them in the side of a filling container, for example.

In the partition 1 of the inside of the filling container used by this invention, as shown to FIGS. 1-4, carrier gas discharge port 3 is carried out from the carrier gas inlet 2 through each space in the filling container. It is characterized by having a partition wall (1) having an opening portion (30) for distributing through).

As an example of the partition 1 provided with this opening part 30, the thing of the structure of FIGS. 5-6 is mentioned, for example.

The positions of these openings 30 are such that the carrier gas sufficiently flows from the carrier gas inlet 2 to the carrier gas outlet 3 through a space filled with the solid organometallic compound, and the filled solid organometallic compound is then There is no particular limitation as long as it is in sufficient contact with the gas and does not interfere with the stable supply of the organometallic compound. Particularly, the opening 30 for flowing the carrier gas may be used to effectively saturate the filled solid organometallic compound with the carrier gas. In the case where the opening portion 30 is disposed below the partition wall 1, 1/3 or less, preferably 1/5 or less, more preferably 1 / of the height inside the container from the inner bottom surface of the filling container. When the opening 30 is provided at a position of 10 or less, and the opening 30 is disposed above the partition 1, the height inside the container from the inner bottom of the filling container. 2/3 or more, Preferably it is 4/5 or more, More preferably, the opening part 30 is provided in the position of 9/10 or more.

The filling container used in the filling method of the present invention is discharged from the carrier gas discharge port 3 by the above structure, and the carrier gas flows through each of the partitioned spaces.

In the filling container used in the present invention, as an example of the partition wall 1 having the openings 30 described above, an example in the case where the partition wall 1 is one sheet, for example, a structure having the structure shown in FIG. In addition, as an example in the case where two partitions 1 are two pieces, the thing of the structure as shown in FIG. 2 appears, for example, and also as an example in the case of three or more partitions 1, for example, FIG. The structure of 3 or 4 can be shown.

Moreover, depending on the position of the opening part 30 provided in the partition 1, the whole space is circulated through the opening part 30 from the carrier gas inlet port 2, and the carrier gas discharge port 3 is carried out. In order to distribute | circulate, it can be set as the structure which provided the flow path 31 in each of the carrier gas introduction port 2 and the carrier gas discharge port 3, respectively. As an example of the filling container which has the structure in which the flow path 31 was formed in each of this carrier gas introduction port 2 and the carrier gas discharge port 3, the thing of the structure shown in FIG. 7, FIG. 8 can be shown, for example. have.

Said flow path 31 is a tubular thing as shown in FIG. 9, for example, what has a flow path lower opening 32 in the lower part of the structure partitioned by the partition 1 like FIG. 10 or FIG. Can be used. The flow path 5 may be a combination of these tubular structures or those having a flow path lower opening 32 in the lower part of the structure partitioned by the partition wall 1.

The position of the flow path lower opening 32 of this flow path 31 is at a position of 1/3 or less, preferably 1/5 or less, more preferably 1/10 or less of the height of the inside of the container from the inner bottom surface of the filling container. It is desirable to install.

The distribution form of the carrier gas in the filling container used by the filling method of this invention is demonstrated based on FIG. First, the carrier gas is introduced from the carrier gas inlet 2 and flows through the space having the carrier gas inlet 2. Carrier gas distributes each space through the opening part 4, is discharged from the carrier gas discharge port 3, and is supplied to MOCVD apparatus. On the other hand, although the distribution form of carrier gas was demonstrated based on FIG. 1, when the filling container is partitioned into three or more spaces, as shown in FIGS. 2-4, the opening part 30 formed in each partition 1, The carrier gas will flow.

In this distribution mode, in the structure in which the flow path 31 is formed in each of the carrier gas inlet 2 and the carrier gas outlet 3 as shown in FIG. 7, the carrier gas is separated from the carrier gas inlet 2. It introduces and distributes the flow path 31, and distributes the inside of the space which has the carrier gas introduction port 2. As shown in FIG. Carrier gas distributes each space through the opening part 30, distributes the flow path 31 formed in the carrier gas discharge port 3, is discharged from the carrier gas discharge port 3, and is supplied to a MOCVD apparatus.

Moreover, in the filling container for solid organometallic compounds used by the filling method of this invention, the filling opening 9 for filling a solid organometallic compound in the space inside the filling container formed by partitioning with the partition 1 is formed. It may be. By forming this filling port 9, it becomes possible to inject a solid organometallic compound in a solid state. In the present invention, the filling port of the filling container can be formed on the top of the filling container, for example, as shown in Figs. In addition, the carrier gas inlet 2 and / or the carrier gas outlet 3 and the carrier gas outlet 3 and the filling port 9 are formed by separating the carrier gas inlet 2 and / or the carrier gas outlet 3 from the filling container. ) Can be used as a structure. The separated carrier gas inlet 2 and / or the carrier gas outlet 3 and the filling container are used again through the connecting parts 26. As an example of this structure, for example, as shown in Fig. 12, between the carrier gas inlet 2 and the filling container, a connecting part 26 that can be separated as a filling port is formed, and it is used again to be used together. Can be mentioned.

On the other hand, in the filling container used in the filling method of the present invention, for example, as shown in Figs. 1 to 4, the valve 22 which can be opened and closed to the carrier gas inlet 2 and the carrier gas outlet 3 is provided. In the case of carrier gas distribution, when the valve 22 is opened and the organometallic compound is not supplied, the solid organometallic compound is contaminated from the outside with the valve normally closed. This prevents sublimation and sublimation outside the filling container.

As described above, in the filling container used in the filling method of the present invention, the inside of the filling container is partitioned into a plurality of spaces by the partition wall 1, and the carrier gas introduced from the carrier gas inlet 2 is filled in each container space. In all the spaces, the solid organometallic compound passes through the top of those spaces to the bottom of the space and flows to the carrier gas outlet 3. In this way, the inside of the container is partitioned into partitions 1 and partitioned into a plurality of spaces, so that the cross-sectional area of each space is reduced, and the contact between the carrier gas and the solid organometallic compound is sufficiently performed. Thus, the carrier is not formed as in the prior art. The state of contact between the gas and the solid organometallic compound can be kept uniform, and the carrier gas makes it possible to stably supply the solid organometallic compound from the filling vessel to the MOCVD apparatus at a constant concentration for a long time, and to control the particle diameter in the vessel. By filling and using a solid organometallic compound, the effect of the particle diameter control can be brought out more effectively.

In the filling method of the present invention, in addition to the filling container for the solid organometallic compound having the above structure, in the filling container for the solid organometallic compound having a carrier gas inlet and a carrier gas outlet, the inside of the filling container is divided into a plurality of vertical spaces. Filled for solid organometallic compounds, characterized in that the carrier gas is fractionated and introduced from the carrier gas inlet by the carrier gas flow direction reversal means to distribute each vertical space in a downward flow and discharge from the carrier gas outlet. A container can be used.

The structure of the above-mentioned filling container which can be used in the present invention is not particularly limited as long as the internal space is divided into a plurality of vertical spaces, and each vertical space flows in a downward flow of carrier gas.

The carrier gas flow direction reversing means of the present invention is a means for reversing the flow direction of the carrier gas in which the fractionated vertical space flows in the downward direction, and supplying the gas flow direction in the downward direction above the adjacent vertical space. Specifically, the carrier gas flow reversing means is provided with a communication flow path formed in the partition as shown in Figs. 13 to 20, and as shown in Figs. 21 and 22, a partition wall is formed by the communication flow path, and Fig. 23. And as shown in FIG. 24, although a communication channel is comprised by a partition, etc. are mentioned, It is not limited to these things.

An example of the filling container for solid organometallic compounds used by this invention is shown to FIGS. 13-16. As shown in FIGS. 13-16, the filling container for solid organometallic compounds used by the filling method of this invention partitions the inside of a filling container in the longitudinal direction by the at least 1 or more partition wall 1, and is at least 2 or more It has a structure partitioned into spaces. The partition system of the space by the partition 1 has a structure in which the space is partitioned, for example, as shown in FIGS. 1 to 4.

The outer shape of the filling container may be, for example, a container having a cylindrical shape such as a triangular prism, a square pillar, a pentagonal pillar, a hexagonal pillar, or the like, in addition to the cylindrical shaped container as shown in FIGS. 13 to 16.

In addition, the filling container for a solid organometallic compound used in the filling method of the present invention has a carrier gas inlet (2) through one space inside the filling container formed by partitioning with the partition wall (1), and passes through one of the remaining spaces. As a structure which has the carrier gas discharge port 3, the thing of the structure of FIGS. 13-16 is mentioned, for example. The carrier gas is introduced from the carrier gas inlet 2 into the filling container filled with the solid organometallic compound, and the inside of the filling container is passed through, and the organic metal compound is discharged from the carrier gas outlet 3 as a gas saturated in the carrier gas. To the MOCVD apparatus. The mounting position of the carrier gas inlet 2 and the carrier gas outlet 3 to the filling container is, for example, depending on the partition system of the space by the partition wall 1, the usage form of the filling container, or the like. May have a structure having a carrier gas inlet 2 and a carrier gas outlet 3, or a structure having them on the side of the filling container, for example.

In the partition 1 inside the filling container of the present invention, as shown in FIGS. 13 to 16, the carrier gas is transferred from the carrier gas inlet 2 to the carrier gas outlet 3 through each space in the filling container. It has a partition 1 having a communication channel 6 having a lower opening 4 and an upper opening 5 for circulating.

In addition, the filling container of the present invention has a structure in which the carrier gas introduced into the filling container is introduced from the lower opening 4 of the communication passage 6 and discharged into the upper opening 5 as shown in FIGS. 13 to 16. Has

Since the filling container of this invention is equipped with the flow path of the said structure, carrier gas distribute | circulates each partitioned space and is discharged | emitted from the carrier gas discharge port 3.

In addition, the filling container of the present invention has a discharge opening having a lower opening 7 for discharging the carrier gas to the carrier gas discharge port 3 from the lower part of the space having the carrier gas discharge port 3 as shown in FIGS. 13 to 16. The flow path 8 is provided.

In the filling container of the present invention, as examples of the communication channel 6 and the channel 8 described above, an example having a structure as shown in FIG. In addition, as an example in the case where two partitions 1 are two pieces, the thing of the structure shown in FIG. 14 appears, for example, and also as an example in the case of three or more partitions 1, for example, FIG. 15 or FIG. The structure of 16 can be shown.

In the filling container for a solid organometallic compound of the present invention, the communication channel 6 may be provided with one or a plurality of tubular ones as shown in FIGS. 17 to 20, for example.

The distribution form of the carrier gas in the filling container of this invention is demonstrated based on FIG. First, the carrier gas is introduced from the carrier gas inlet 2 and descends into the space having the carrier gas inlet 2. Carrier gas flows in from the lower opening part 4 of the communication flow path 6 as a carrier gas flow direction reversal means near the bottom of the container, flows through the communication flow path 6 as an upflow, and discharges the carrier gas outlet. It is fed to the top of the space with (3). The carrier gas supplied to the top of the space having the carrier gas outlet 3 descends. The discharge passage 8 is raised from the lower opening 7 of the discharge passage 8 near the lower portion of the space having the carrier gas outlet 3, discharged from the carrier gas outlet 3, and supplied to the MOCVD apparatus. do. On the other hand, although the distribution form of carrier gas was demonstrated based on FIG. 13, when the filling container inside is divided into three or more spaces, as shown in FIGS. 14-16, it connects to the communication flow path 6 formed in each partition 1, As a result, the carrier gas flows through each space as a downward flow from the upper side to the lower side.

For example, the same effect is achieved even if the partition 1 has a structure which also serves as the communication channel 6 as shown in FIGS. 21 to 24. As these structures, for example, as shown in Fig. 21, the tubular structures are lined up in the longitudinal direction of the container, and the gaps are closed in the form in which the tubular structures are in contact with each other, or as shown in Figs. Likewise, the gap between the tubular structures is formed by the partition wall 1, and an opening is formed in the lower portion of the tubular structure on the upstream side with respect to the carrier gas flow direction, and the lower opening 4 is formed downstream. An opening is formed in the upper portion of the tubular structure on the side of the space on the side, and the opening is formed as the upper opening 5, and as shown in FIG. 23 or 24, two partitions 1 are provided upstream with respect to the carrier gas flow direction. Even if an opening is formed in the lower part of the partition 1 on the side of the space side, and this is made into the lower opening part 4, and an opening is formed in the lower part of the partition 1 of the downstream side of the space side, and this is made into the upper opening part 5, do. The communication channel 6 may be one of these tubular structures or a combination of a structure in which the partition wall 1 serves as the communication passage 6.

Moreover, in the filling container of this invention, also about the discharge flow path 8 which has the lower opening part 7 which discharges a carrier gas to the carrier gas discharge port 3 from the lower part of the space which has the carrier gas discharge port 3, For example, a tubular structure having an opening in the lower portion as shown in FIG. 25, or having a lower opening 7 in a lower portion of the structure partitioned by the partition wall 1 as shown in FIG. 26 or 27. Can be used. The discharge passage 8 may be a combination of these tubular structures or those having a lower opening 7 below the structure partitioned by the partition wall 1.

Moreover, in the filling container for solid organometallic compounds of this invention, the space which has the communication flow path 6 and carrier gas discharge port 3 which have the lower opening part 4 and the upper opening part 5 for flowing each carrier gas, In the discharge passage 8 having the lower opening 7 for discharging the carrier gas from the lower part to the carrier gas outlet 3, the positions of the upper opening 5 and the lower opening 4 are determined by the solid organometallic compound. The carrier gas is discharged from the carrier gas inlet 2 through the discharge passage 8 having the filled space or the communication passage 6 and the lower opening 7 through which the carrier gas is discharged to the carrier gas outlet 3. There is no restriction | limiting in particular if it is a position which fully distribute | circulates to the discharge port 3, and the solid organometallic compound charged at that time is in sufficient contact with a carrier gas, and does not interfere with the stable supply of an organometallic compound, In the communication passage 6 having the lower opening 4 and the upper opening 5 for flowing the carrier gas, in order to effectively saturate the filled solid organometallic compound with the carrier gas, the lower opening 4 is filled. It is installed at a position of 1/3 or less, preferably 1/5 or less, more preferably 1/10 or less, from the inner bottom of the vessel, and the upper opening 5 is located from the inner bottom of the filling vessel. The carrier gas is installed at a position of at least 2/3, preferably at least 4/5, more preferably at least 9/10 of the height inside the vessel, and the carrier gas is discharged from the lower portion of the space having the carrier gas outlet 3. In the discharge passage 8 having the lower opening 7 discharged to the bottom, the lower opening 7 is 1/3 or less, preferably 1/5 or less, more preferably 1/5 or less of the inner height of the container from the inner bottom surface of the filling container. Preferably 1 It is preferable to install at a position of / 10 or less.

When the solid organometallic compound is filled into the filling container of the present invention and used for supplying the organometallic compound to the MOCVD apparatus, the solid organometallic compound is filled into the space inside the filling container.

Moreover, in the filling container for solid organometallic compounds of this invention, the filling opening 9 for filling a solid organometallic compound in the space inside the filling container formed by partitioning with the partition 1 can also be formed. By forming this filling port 9, it becomes possible to inject a solid organometallic compound in a solid state. In the present invention, the filling port of the filling container can be formed in the upper portion of the filling container, for example, as shown in Figs. In addition, the carrier gas inlet 2 and / or the carrier gas outlet 3 and the carrier gas outlet 3 and the filling port 9 are formed by separating the carrier gas inlet 2 and / or the carrier gas outlet 3 from the filling container. ) Can be used as a structure. The separated carrier gas inlet 2 and / or the carrier gas outlet 3 and the filling container are used again through the connecting parts 26. At this time, the flow path 8 connected to the carrier gas discharge port 3 also has a structure in which the flow path 8 can be detached, thereby facilitating the filling of the solid organometallic compound. As an example of this structure, for example, as shown in Fig. 28, between the carrier gas inlet 2 and the filling container, a connecting part 26 that can be separated as a filling port is formed, and it is used again to be used together. Can be mentioned.

On the other hand, in the filling container of the present invention, for example, as shown in Figs. 13 to 16, the carrier gas inlet 2 and the carrier gas outlet 3 can be provided with a valve 22 that can be opened and closed, In the case of carrier gas distribution, when the valve 22 is opened and the organometallic compound is not supplied, the solid organometallic compound is contaminated from the outside with the valve normally closed or outside the filling container. Prevents sublimation and multiplication

As described above, in the filling container used in the filling method of the present invention, the inside of the filling container is partitioned into a plurality of spaces by the partition wall 1, and the carrier gas introduced from the carrier gas inlet 2 is placed in each container space. The filled solid organometallic compound passes through the upper portion of the space from the upper portion of the space to the lower portion of the space and flows to the carrier gas outlet 3. In this way, the inside of the container is partitioned into partitions 1 and partitioned into a plurality of spaces, so that the cross-sectional area of each space is reduced, and the contact between the carrier gas and the solid organometallic compound is sufficiently performed. Thus, the carrier is not formed as in the prior art. The state of contact between the gas and the solid organometallic compound can be kept uniform, and the carrier gas makes it possible to stably supply the solid organometallic compound from the filling vessel to the MOCVD apparatus at a constant concentration for a long time, and to control the particle diameter in the vessel. By filling and using a solid organometallic compound, the effect of the particle diameter control can be brought out more effectively.

When the solid organometallic compound is filled into the filling container by the method of filling the solid organometallic compound into the filling container for the solid organometallic compound of the present invention, and used for supplying the organometallic compound to the MOCVD apparatus, the inside of the filling container Fill the space with a solid organometallic compound.

In the method for filling a solid organometallic compound into a filling container for a solid organometallic compound of the present invention, as a method for filling a solid organometallic compound in a space inside the filling container, a method known so far can be used as it is. For example, a method of introducing and filling a solid organometallic compound into a filling container by sublimation, or, for example, a method of introducing and filling an organometallic compound into a filling container as saturated vapor in a carrier gas; In addition, for example, a method of heating the organometallic compound to a melting point or more and introducing the same into a filling container may be used. However, these methods are difficult to control the particle diameter of the solid organometallic compound. There are many.

Usually, in the filling of the solid organometallic compound which controlled the particle diameter of this invention to the filling container for solid organometallic compounds, the solid organometallic compound is made into the space inside a filling container, without requiring the special operation as mentioned above. By using the filling container which provided the filling opening for filling, the solid organometallic compound which controlled the particle diameter from the outside of a filling container can be thrown in solid state.

When the solid organometallic compound is, for example, a substance that ignites in air, the filling operation from the filling port of the solid organometallic compound described above is performed with respect to a solid organometallic compound such as nitrogen, argon, helium, and the like. It can be performed in an atmosphere of inert gas.

About the solid organometallic compound which can be filled and used for the filling container of this invention, not only the solid organometallic compound used by the filling container known so far but also other solid organometallic compound, supply use temperature using a carrier gas, In terms of pressure, it is applicable that there is a saturated vapor pressure that can be met for the desired feed for the carrier gas and that it is solid under the feed conditions. Representative examples of these solid organometallic compounds include alkyl metal compounds, metallocene compounds, β-diketone complexes, and adduct compounds. Specific examples thereof include trimethylindium and dimethylchloro. Alkyl metal compounds such as indium, triphenylaluminum, triphenylbismuth, tert-butyllithium, cyclopentadienyl indium, biscyclopentadienyl magnesium, biscyclopentadienyl manganese and ferrocene , Barium acetylacetonate complex, strontium acetylacetonate complex, copper acetylacetonate complex, calcium acetylacetonate complex, barium dipyvaloyl methate complex, strontium dipyvaloyl methate complex, copper dipivaloyl methate complex, yttrium Β-diketone complexes such as dipivaloyl methate complex, calcium dipivaloyl methate complex, and trimethyl phosphorus And trimethyl arsine air ducts, there may be mentioned trimethyl indium-trimethyl phosphine and air ducts, air ducts compounds such as barium carbonate and Diffie fours days meth 1,10-phenanthroline (phenanthroline) air ducts and the like.

In addition, the pressure at the time of using the filling container which filled the solid organometallic compound with the filling method of this invention can be used, without changing the conditions currently used by the filling container known so far, and the solid organometallic compound is stably MOCVD for a long time. There is no restriction | limiting in particular if it is a condition supplied to an apparatus, Although any of pressurization, normal pressure, and reduced pressure can be used, it is normally used on the conditions of pressure reduction from the vicinity of normal pressure.

Moreover, about the temperature at the time of using the filling container which filled the solid organometallic compound with the filling method of this invention, it is applicable without changing the conditions currently used by the filling container known so far, and the solid organometallic compound used normally For this carrier gas, a condition in which a saturated vapor pressure is obtained which can be met for a desired supply and becomes solid under the supply conditions is applicable.

In the filling container filled with the solid organometallic compound by the filling method of the present invention, any carrier gas that is used in a known filling container can be used, for example, inert gas such as nitrogen, argon, helium or the like. Hydrogen gas or the like can be used.

Moreover, in the filling container which filled the solid organometallic compound by the filling method of this invention, the well-known filler used by filling with a solid organometallic compound in the filling container known so far can be used. As this filler, stainless steel, glass, ceramics, a fluororesin, etc. are used as the material, Preferably, stainless steel can be used. As the shape of the filler, various shapes such as round, square, cylindrical, coil, spring, and spherical shapes can be used. For example, various examples of distillation packing, for example, Dixon packing, can be used. , Helipack, penske, etc. can be used. Fibrous fillers can also be used.

In the present invention, the size of the filler can be a size that passes through the size of the opening of the filling port provided in the filling container, and is usually 0.8 to 8 mm, preferably 0.8 to 6 mm, more preferably 0.8. What is-5 mm can be used.

In the filling container of this invention, these fillers can also be filled with a filling container by the method known so far, and can be used with a solid organometallic compound.

On the other hand, the filling method of the present invention can be used not only for the solid organometallic compound but also for the filling of general solid materials such as solid inorganic compounds, solid organic compounds, or solid metals having a vapor pressure. Thus, the filling method of this invention can be used also as a filling method for discharging other solid substance instead of a solid organometallic compound as a gas saturated with a carrier gas using a carrier gas.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail according to an Example.

≪ Example 1 >

Trimethylindium was used as the solid organometallic compound.

Trimethyl indium was pulverized in a nitrogen atmosphere, and the particle diameter of trimethyl indium was set to 4.75 mm or less using a sieve having a sieve hole of 4.75 mm. Moreover, the particle diameter of trimethyl indium was cut into the thing of 1 mm or less using the sieve which has a 1-mm sieve hole from the particle | grains of trimethyl indium whose particle diameter which passed this sieve is 4.75 mm or less, and cuts the particle diameter of 4.75 mm or less Trimethyl indium having was prepared.

As a result of checking the particle diameter of this trimethyl indium particle, 50% or more of it was the magnitude | size of 2.5-4.75 mm.

Supply stability was tested using the trimethyl indium containing the particle | grains obtained in this way and the particle | grains of 2.5-4.75 mm.

The test of supply stability was done with the following method.

In a nitrogen atmosphere, 200 g of trimethylindium and 263 g of 0.9 mm × 1.8 mm × 1.8 mm stainless steel filler having a particle diameter controlled by the method described above in a SUS filling container having an outer diameter of 60.5 mm phi as shown in FIG. 28. And 97 g of stainless steel filler of 2.5 mm × 5.0 mm × 5.0 mm were filled from the filling port 9. In this filling operation, it separated from the connection part 26 part, and made it into the charging port 9, and filled it.

Next, the carrier gas outlet 3 was connected to a trap cooled with dry ice methanol for trimethyl indium collection. The piping connecting the carrier gas outlet 3 and the trap cooled by dry ice-methanol was heated, and trimethyl indium did not precipitate in this piping. The filling container containing trimethyl indium and a filler was immersed in a 25 degreeC thermostat, and nitrogen gas was discharged from the carrier gas inlet 2 of a filling container on the conditions which made the pressure in the apparatus system of a supply stability test into the vicinity of atmospheric pressure. The weight of trimethyl indium collected in the trap cooled by 500 cc every minute and cooled with dry ice methanol every 8 hours was measured. In addition, the gas phase gas concentration of the carrier gas containing the vapor of trimethyl indium was measured with the ultrasonic type gas concentration meter (brand name Epison: product of Thomas Swan Corporation).

The results are shown in Fig. In the vertical axis of the graph shown in FIG. 29, the supply amount of trimethyl indium per hour was shown on the vertical axis, and the use ratio of trimethyl indium supplied on the horizontal axis was expressed in% by weight.

As a result of the test of supply stability, when the filling method of the present invention was used, the supply rate of trimethylindium was stable up to 91% by weight of the use ratio.

Thus, by using the particle diameter of a solid organometallic compound containing the particle | grains whose particle diameter is 2.5-4.75 mm, supply of a solid organometallic compound can be performed stably at a constant density | concentration, and the stable supply rate is obtained It becomes possible to increase the use ratio of a solid organometallic compound under conditions. As a result, the period of supplying a solid organometallic compound stably can be improved.

≪ Comparative Example 1 &

In Example 1, trimethyl indium was grind | pulverized in nitrogen atmosphere, and operation similar to Example 1 except having made trimethyl indium into the particle | grains of 2.36 mm or less of particle diameters using the sieve which has a sieve hole of 2.36 mm is carried out. Was performed to test the supply stability of the solid organometallic compound. The results are shown in Fig. The use amount of trimethyl indium per hour was shown on the vertical axis of the graph shown in FIG. 30, and the use ratio of trimethyl indium supplied on the horizontal axis was shown by weight%. As a result of the test of supply stability, the supply rate of the trimethyl indium which does not contain the particle | grains whose particle diameter is 2.5-6 mm was stable up to 77 weight% of the use ratio.

Thus, when the trimethyl indium which does not contain the particle | grains of trimethyl indium whose particle diameter is 2.5-6 mm was used, it was not able to obtain a supply rate stably for a long time like Example 1.

<Example 2>

In Example 1, the filling container was made into a SUS filling container having an outer diameter of 76 mm phi as shown in FIG. 28, and 400 g of trimethylindium and 0.94 mm x 1.8 mm x 1.8 mm stainless steel filler having a particle diameter controlled. Except having used 78 g of 2.5 mm * 5.0 mm * 5.0 mm stainless steel fillers, operation similar to Example 1 was performed and the supply stability of the solid organometallic compound was tested. The results are shown in Fig. In the vertical axis of the graph shown in FIG. 31, the supply amount of trimethyl indium per hour was shown on the vertical axis, and the use ratio of trimethyl indium supplied on the horizontal axis was expressed in% by weight. As a result of the test of supply stability, the supply rate of the trimethyl indium containing the particle | grains whose particle diameter is 2.5-6 mm was stable to 85 weight% of the use ratio.

<Example 3>

In Example 1, the filling container was made into the glass filling container of the outer diameter 35mm (phi) which has the structure which removed the diffuser 20a from the container of the structure as shown in FIG. 34, and used 100 g of trimethyl indium which controlled the particle diameter. The same operation as in Example 1 was carried out except that the supply stability of the solid organometallic compound was tested. As a result of the test of supply stability, the supply rate of the trimethyl indium containing the particle | grains whose particle diameter is 2.8-4.75 mm was stabilized to 76 weight% of the use ratio.

Comparative Example 2

In Example 2, trimethyl indium was pulverized in a nitrogen atmosphere, and operation similar to Example 1 was carried out except that trimethyl indium was made into particles having a particle diameter of 2.36 mm or less using a sieve having a body hole of 2.36 mm. Was performed to test the supply stability of the solid organometallic compound. The results are shown in Fig. The vertical axis of the graph shown in FIG. 32 shows the supply amount of trimethyl indium per hour on the vertical axis, and the use ratio of the trimethyl indium supplied on the horizontal axis is shown by weight%. As a result of the test of supply stability, the supply rate of the trimethyl indium which does not contain the particle | grains whose particle diameter is 2.5-6 mm was stable to 59 weight% of the use ratio.

Thus, when the trimethyl indium which does not contain the particle | grains of trimethyl indium whose particle diameter is 2.5-6 mm was used, it was not able to obtain a feed rate stably for a long time like Example 2.

&Lt; Comparative Example 3 &

In Example 3, operation similar to Example 3 was performed except that trimethyl indium was grind | pulverized in nitrogen atmosphere and trimethyl indium was made into the particle | grains of 0.1-0.3 mm of particle diameters, and supply stability of a solid organometallic compound was carried out. Tested. As a result of the test of supply stability, the supply rate of the trimethyl indium which is particle | grains whose particle diameter is 0.1-0.3 mm was stable up to 20 weight% of the use ratio.

Thus, when trimethyl indium of the particle | grains whose particle diameters are 0.1-0.3 mm was filled and used, supply speed could not be obtained stably for a long time like Example 3.

2: carrier gas inlet port 3: carrier gas outlet port
9: filling port 22: valve
26: connection part 2a: carrier gas inlet
3a: carrier gas outlet 7a: lower opening
8a: Euro 9a: charging port
20a: diffuser 21a: solid organometallic compound batch chamber
22a: valve 23a: columnar container
24a: filter 25a: inlet chamber
27a: porous member

Claims (4)

A method of filling trimethylindium into a filling container for trimethylindium to include particles having a particle diameter of 2.5 to 4.75 mm consisting solely of trimethyl indium in the trimethyl indium, and also having the particle diameter of 2.5 to 4.75 mm per trimethyl indium. A method of filling trimethylindium into a filling container for trimethylindium, comprising the step of charging the trimethylindium to the filling container for trimethylindium so that the proportion of particles is 50 to 100%. The method of filling trimethylindium according to claim 1, wherein a filler is further coexisted with the trimethylindium. The filling method of trimethyl indium according to claim 2, wherein the filler has a size of 0.8 to 8 mm. The filling container for trimethyl indium which filled trimethyl indium by the filling method in any one of Claims 1-3.

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