Method and container for filling solid organometallic compound

Filling method of trimethyl indium and filling container

The present invention relates to a filling method for a filling container of a solid organometallic compound and a filling container of a solid organometallic compound filled by the filling method. In more detail, it is about solid organic materials that can be used for vapor phase epitaxy growth based on the Metalorganic Chemical Vapor Deposition (hereinafter referred to as "MOVCD") method used in the manufacture of compound semiconductors and other materials for the electronics industry. A method for filling a filling container with a solid organometallic compound and a filling container filled with a solid organometallic compound by the filling method of a solid organometallic compound in a filling container and a filling container filled with a solid organometallic compound in a gas phase epitaxial growth apparatus stably supplied at a constant concentration for a long period of time.

Organometallic compounds such as trimethylindium are widely used as raw materials when manufacturing materials for the electronics industry.

As a manufacturing method of materials for the electronics industry using organometallic compounds, vapor phase epitaxial growth based on the MOCVD method or the like has been mostly used in recent years. For example, a thin film of compound semiconductor is produced by the MOCVD method. In this case, an organometallic compound such as trimethylaluminum, trimethylgallium, and trimethylindium is used as a raw material.

When these organometallic compounds are used by the MOCVD method, the conditions used for the organometallic compounds are usually used in the case of solids: the organometallic compound is filled with the carrier gas inlet (2a) and carrier as shown in Figure 33 The filling container of the gas outlet (3a) (hereinafter referred to as Fill the container A), introduce a carrier gas such as hydrogen into the container from the carrier gas inlet (2a), take out the organometallic compound as a gas saturated in the carrier gas from the carrier gas outlet (3a) and supply it to the MOCVD device method.

At this time, when the organometallic compound is solid at the temperature used for the above-mentioned supply, the following problem will occur: the carrier gas formed in the solid organometallic compound in the filling container A cannot sufficiently interact with the solid organometallic compound. The flow path that the organometallic compound directly passes through makes it difficult to maintain the contact state of the carrier gas and the solid organometallic compound evenly, and it is not easy to use the carrier gas to stably supply the solid organometallic compound from the filling container A at a certain concentration for a long period of time. To the MOCVD device. In addition, in the supply of the solid organometallic compound according to the method using the aforementioned carrier gas, when the amount of the solid organometallic compound filled in the filling container A is gradually increased, the amount of the solid organometallic compound that is stably supplied to the MOCVD device The ratio of is reduced to the amount of solid organometallic compound that has been filled. As a result, the residual amount of the solid organometallic compound in the filling container increases, and the problem that the solid organometallic compound cannot be used effectively is caused.

In order to solve these problems, various methods for filling the container A with a solid organometallic compound have been proposed. For example, in Patent Document 1, Patent Document 2, Patent Document 3, Patent Document 4, and Patent Document 5, a method of filling a filling container with a solid organometallic compound and a filler is proposed. In addition, for example, in Patent Document 6, it is proposed to coat a solid organometallic compound on a support of an inert gas, and fill it in a filling container. DeviceA method.

In addition, in order to solve the aforementioned problems, various proposals have been made regarding the structure of the filling container itself filled with solid organometallic compounds. For example, in Patent Document 7, as shown in Fig. 34, a diffuser (20a) for equalizing the gas is installed at the carrier gas inlet, and a filling container (hereinafter Called the filling container B).

In addition, for example, Patent Document 8 proposes a filling container (hereinafter referred to as filling container C) of a gas-permeable solid organometallic compound installation chamber (21a) as shown in Fig. 35.

In addition, for example, Patent Document 9 proposes a filling container (hereinafter referred to as filling container D) in which a porous entrance chamber as shown in Fig. 36 is used as a filling part of a solid organometallic compound.

On the one hand, Patent Document 10 proposes a method for stabilizing the supply of a solid organometallic compound and controlling the particle size when a ruthenium compound is used.

[Patent Document 1] Special Publication No. 5-39915 [Patent Document 2] Special Publication No. 6-20051 [Patent Document 3] Japanese Patent Application Publication No. 7-58023 [Patent Document 4] JP 8-250440 A [Patent Document 5] JP 8-299778 A [Patent Document 6] Patent No. 2651530 [Patent Document 7] Japanese Patent Publication No. 2-124796 [Patent Document 8] JP 10-223540 A [Patent Document 9] JP 2002-83777 A [Patent Document 10] JP 2003-160865 A

<p>However, the filling methods and filling container proposals in Patent Documents 1 to 9 have not reviewed the particle size of the solid organometallic compound itself filled into the filling container.</p><p>In addition, Patent Document 10 regarding the influence of the particle size control of the ruthenium compound on the stability of the supply, the effect of the initial state of the supply is explained based on the review of several film formation, but it does not clearly describe the stability of the ruthenium compound at a constant concentration for a long period of time. The effect of land supply. As a result of the review of the present inventors, it was found that in the supply of solid organometallic compounds using a carrier gas, there is a particle size control method that can obtain not only initial stability but also long-term stability.</p><p>The present invention was developed to solve the aforementioned problems, and its object is to provide a solid organometallic compound for filling a container that can stably supply a solid organometallic compound to a vapor-phase epitaxial growth device at a constant concentration for a long period of time. A filling method and a filling container filled with a solid organometallic compound by the filling method.</p>

<p>In order to solve the aforementioned problems, the present inventors have reviewed the results and found that in order to fill the filling container with a solid organometallic compound, the solid organometallic compound is supplied at a constant concentration for a long period of time by circulating a carrier gas. When the solid organometallic compound is filled in the solid organometallic compound filling container, the particle size of the solid organometallic compound is controlled to a certain characteristic. The particle size below a certain size can not only ensure the initial supply stability, but also can maintain the supply stability for a long period of time, thus completing the present invention.</p><p>That is, regarding a method of filling trimethylindium in a filling container for trimethylindium, it is characterized in that when filling trimethylindium in the filling container for trimethylindium, only The particles composed of trimethylindium are particles with a particle size of 8 mm or less. Furthermore, trimethylindium must contain particles with a particle size of 2.5-6 mm.</p><p>In addition, in the filling method of the present invention, trimethylindium with a controlled particle size can be used in coexistence with the filler, which is a filling container for solid organometallic compounds. The method of filling a solid organometallic compound is aimed at the method of filling a solid organometallic compound field in a filling container for a solid organometallic compound, characterized in that the particle size of trimethylindium is 8 mm or less, and further Trimethyl indium must contain particles with a particle size of 2.5-6 mm.</p><p>And, in the filling method of trimethylindium for the filling container for trimethylindium, the trimethylindium and the filling material are filled together, and the filling material with a size of 0.8-8 mm is used.</p><p>In addition, in the method of filling trimethylindium for a filling container for trimethylindium, the filling container for trimethylindium has the following structure: Filling container for trimethyl indium carrying 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 flows through each of the vertical spaces, and is discharged from the carrier gas outlet.</p><p>In addition, in the filling method of the filling container for trimethyl indium, the filling container for trimethyl indium can have the requirements (a) to (c): (a) at least one The partition wall divides the inside of the filling container in the longitudinal direction, and the inside of the filling container is divided into at least two spaces; (b) The space inside the filling container formed by partitioning by the partition has: Possess The space of the carrier gas inlet and the space provided with the carrier gas discharge port; (c) The partition inside the filling container is equipped with: a space for the carrier gas to flow from the carrier gas inlet through each space in the filling container to The partition wall that carries the opening of the gas discharge port.</p><p>Regarding the aforementioned filling container for solid organometallic compounds, those having the requirements (a) to (c) are provided in the opening part, when the opening part is provided in the lower part of the partition wall , The opening is provided at a position less than 1/3 of the height of the container from the inner bottom surface of the filling container, and when the opening is provided on the upper part of the partition wall, the opening is provided at a position calculated from the inner bottom surface of the filling container Lift at a position above 2/3 of the internal height of the container.</p><p>And, the filling method of trimethyl indium in the filling container for trimethyl indium , For the aforementioned filling container for trimethyl indium, it is equipped with (a)~( Requirement of c), wherein a filling port for filling trimethylindium is provided in the space inside the filling container formed by partitioning it with a partition wall.</p><p>In addition, in the filling method of trimethyl indium in the filling container for trimethyl indium, the filler for trimethyl indium is trimethyl indium with a carrier gas inlet and a carrier gas discharge port. The filling container for indium is characterized in that it has the following structure: 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 used as the carrier gas by means of reversing the direction of carrier gas flow. The reverse flow circulates in each vertical space and is discharged from the carrier gas discharge port.</p><p>In addition, the method for filling trimethylindium in a filling container for trimethylindium of the present invention is characterized in that the filling container for trimethylindium is characterized in that: Requirements: (d) A structure in which the inside of the filling container is divided in the longitudinal direction by at least one partition wall, and the inside of the filling container is divided into at least two or more spaces; Filled volume The space inside the container includes: a space with a carrier gas inlet and a space with a carrier gas discharge port; (f) a partition wall inside the filling container includes: a partition wall with a connecting flow path, the connecting flow path having It is used to make the carrier gas circulate from the carrier gas inlet through the spaces in the filling container to the carrier gas outlet The lower opening and the upper opening; (g) In the communication passage, the carrier gas introduced into the filling container is introduced from the lower opening of the connecting flow path and discharged to the upper opening; (h) It has a structure with a lower opening The discharge flow passage of the mouth, the lower opening part discharges the carrier gas from the lower part of the space with the carrier gas discharge port to the carrier gas discharge port.</p><p>In addition, in the filling method of trimethylindium for the filling container for trimethylindium of the present invention, for the aforementioned filling container for trimethylindium, those having the requirements (d) to (h), which In the aforementioned connecting flow passage, the lower opening of the connecting flow passage is provided at a position less than 1/3 of the height of the container from the inner bottom surface of the filling container, and the upper opening of the connecting flow passage is provided by the filling container. In the position above 2/3 of the height of the inside of the container from the inner bottom surface of the container, in the aforementioned discharge flow path, the lower opening of the discharge flow path is set at 1/th of the height of the inside of the container calculated from the inner bottom surface of the filling container. 3 to Location.</p><p>In addition, the filling method of trimethyl indium in the filling container for trimethyl indium is for those having the requirements (d) to (h) in the aforementioned filling container for trimethyl indium. The space inside the filling container formed by partitions has a filling port for filling trimethylindium.</p><p>In addition, the present invention relates to a filling container for trimethylindium filled with trimethylindium by the filling method of the present invention.</p><p>According to the present invention, when the solid organometallic compound is filled in the filling container for the solid organometallic compound, the particle size of the solid organometallic compound must contain a certain Particles of a specific size can not only ensure the initial stability, but also can stably supply the solid organometallic compound to a vapor phase epitaxial growth device such as a MOCVD device for a long period of time.</p>

The following describes in detail the filling method of the present invention and the filling container for filling the solid organometallic compound by the filling method.

The filling method of the present invention is characterized in that when the solid organometallic compound is filled in the filling container for the solid organometallic compound, the solid organometallic compound is The particle size is 8 mm or less, and the solid organometallic compound must contain particles with a particle size of 2.5-6 mm.

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 formed by the filling provided in the filling container. The size of the mouth opening can usually be 8 mm or less, ideally 6 mm or less, more preferably 5 mm or less, and the solid organometallic compound must contain particles with a particle size of 2.5-6 mm or less.

When the solid organometallic compound exceeds 8 mm, when the carrier gas flow rate is increased, the contact area of the carrier gas and the solid organometallic compound is reduced. , So it becomes impossible to obtain sufficient time to reach saturation. Therefore, long-term supply stability cannot be obtained.

In addition, the ratio of particles of 2.5-6 mm per solid organometallic compound is, for example, 30-100%, ideally 40-100%, more preferably 50-100%.

This is because when the existence ratio of particles of 2.5-6 mm per solid organometallic compound is small, for example, when a large number of particles larger than 6 mm are contained, the flow rate of the carrier gas increases, and it cannot be obtained. The sufficient contact between the carrier gas and the solid organometallic compound particles makes it impossible to obtain long-term supply stability. In addition, this is because, for example, when a large number of particles smaller than 2.5 mm are contained, the contact area between the carrier gas and the particles becomes larger, so that the initial supply stability can be obtained well, but when used for a long period of time, As the solid organometallic compound is gradually consumed as a saturated vapor supplied to the carrier gas, the particles become smaller, and the carrier gas is difficult to pass through the small particles. The phenomenon that the carrier gas passes through the larger particles becomes easier to form a solid. The phenomenon that the organometallic compound and the carrier gas pass through the flow path without sufficient contact is caused by long-term use, and the result of supply stability cannot be obtained.

The method for forming the particles of the solid organometallic compound is not particularly limited, and conventionally known forming methods can still be used. As an example of this forming method, for example, a method of crushing a block of a solid organometallic compound, a method of liquefying a solid organometallic compound and then solidifying it, etc. can be used.

In addition, the method of controlling the particle size of the solid organometallic compound is not particularly limited, and the well-known method of making the particle size uniform can be used. As a method of controlling the particle size, for example, pulverizing solid The method of lumps of organometallic compounds, the method of pulverizing the solid organometallic compound, and the method of recovering those passing through a certain size of sieve with a sieve, etc., for example, the method of solidifying the solid organometallic compound after liquefying to control the droplets The weight method, or the use of a template, the method of controlling the shape of the liquid with the size of the template, etc.

The aforementioned method is not particularly limited as a method for obtaining a solid organometallic compound with a particle size of 8 mm or less, and the solid organometallic compound must contain particles with a particle size of 2.5-6 mm. In other words, it can be used: for example, the moderately pulverized solid organometallic compound can be sieved through and cannot pass through a sieve with a mesh size of 8 mm, and the solid organometallic compound below 8 mm after the sieving can be further moderately pulverized, After passing it through a sieve with a mesh size of 6 mm, separating the particles that have not passed the sieve size of 2.5 mm to obtain a solid organometallic compound of particles with a particle size of 2.5-6 mm, the particle size is 2.5~ A method where 6 mm particles are an essential ingredient in a solid organometallic compound, mixed to a solid organometallic compound particle below 8 mm obtained by passing through a sieve with a mesh size of 8 mm, or the total amount is recovered to moderately pulverize It is a method in which a simple solid organometallic compound containing particles with a particle size of 2.5-6 mm is passed through a sieve with a size of 2.5-6 mm.

In this way, in the method of filling the solid organometallic compound in the filling container to circulate the carrier gas, the solid organometallic compound has a particle size of 8 mm or less, and the solid organometallic compound must contain a particle size of 2.5-6 mm particles can be supplied at a certain concentration for a long period of time The reason for the effect of the solid organometallic compound is that it must contain particles with a particle size of 2.5-6 mm. The space formed by the particles of this size forms a carrier gas that can easily circulate. When the diameter does not contain particles of 25-6 mm, although the solid organometallic compound is in the solid organometallic compound at the initial stage of the supply of the solid organometallic compound, sufficient contact between the carrier gas and the solid organometallic compound can be obtained, but it will be used for a long period of time. , It is easy to form a flow path through which the carrier gas does not fully contact the solid organometallic compound directly.

Therefore, when the solid organometallic compound is supplied with a carrier gas, when the particle size of the solid organometallic compound does not include particles with a particle size of 2.5-6 mm, there will be no problem with the initial supply stability, but Long-term stability will produce flaws. According to the present invention, by using particles with a particle size of 2.5-6 mm that must contain the solid organometallic compound in the solid organometallic compound, it becomes difficult to form a flow path, which not only stabilizes the short-term supply, but also enables The carrier gas circulates stably in the filling layer of the solid organometallic compound for a long period of time, thereby improving the supply stability of the solid organometallic compound.

In the filling method of the present invention, the filling container for the solid organometallic compound that can be used is not particularly limited, and for example, the well-known container as described above can be used as it is.

Furthermore, in addition to the filling container for solid organometallic compounds of the aforementioned structure, the filling method of the present invention can also be used in a filling container for solid organometallic compounds having a carrier gas inlet and a carrier gas discharge port. It is characterized by: It has the following structure: the inside of the filling container is Divided into a plurality of vertical spaces, the carrier gas introduced through the carrier gas inlet circulates through each vertical space, and the solid organometallic compound is filled out by the carrier gas outlet.

An example of this solid organometallic compound filling container is shown in Figures 1 to 4. As shown in Figures 1 to 4, the filling container for solid organometallic compounds used in the filling method of the present invention has at least one partition wall (1) partitioning the inside of the filling container in the longitudinal direction, and is divided into The structure of at least 2 or more spaces. According to the partitioning method of the space of the partition wall (1), there are, for example, a structure that partitions the space as shown in FIGS. 1 to 4.

The outer shape of the filling container can be made into a cylindrical container as shown in Figures 1 to 4, but can also be made into a triangular column, a quadrangular column, a pentagonal column, a hexagonal column, and the like.

In addition, the structure of the filling container for solid organometallic compounds used in the filling method of the present invention is a carrier gas inlet (2) communicating with one of the spaces in the filling container formed by partitioning the partition (1) , And has a carrier gas discharge port (3) connected to one of the remaining spaces, for example, the structure shown in Figures 1 to 4 can be cited. The carrier gas is introduced into the filling container filled with the solid organometallic compound from the carrier gas inlet (2), so that it circulates inside the filling container, and the carrier gas outlet (3) uses the organometallic compound as saturated in the carrier gas The gas is taken out and supplied to the MOCVD device. The carrier gas inlet (2) and carrier gas outlet (3) are arranged in the filling container according to the partitioning method of the partition wall (1) or the use form of the filling container. For example, in the filling container The upper part has a carrier gas inlet (2) and the structure of the carrier gas discharge port (3), or these structures installed on the side of the filling container.

The partition wall (1) inside the filling container used in the present invention, as shown in Figures 1 to 4, is characterized by being equipped with a carrier gas through the carrier gas inlet (2) through the filling container Each space circulates to the partition wall (1) of the opening (30) of the carrying gas discharge port (3).

As an example of the partition wall (1) provided with this opening part (30), for example, the structurer of FIGS. 5-6 can be mentioned.

The position of these openings (30), if the carrier gas is filled with a solid organometallic compound, the carrier gas inlet (2) can sufficiently circulate to the carrier gas outlet (3). At this time, the filled solid The organometallic compound is in full contact with the carrier gas, and there is no particular limitation as long as it does not cause an obstacle to the stable supply of the organometallic compound, but it is especially effective for the filled solid organometallic compound and the carrier gas. The ground saturation contact lies in the opening (30) used to circulate the carrier gas. When the opening (30) is provided in the lower part of the partition wall (1), the height of the inside of the container is calculated from the inner bottom surface of the filling container. The opening (30) is provided at a position less than 1/3, ideally 1/5 or less, and more preferably 1/10 or less. When the opening (30) is provided on the upper part of the partition wall (1), the An opening (30) is provided at a position where the height of the interior of the container from the inner bottom surface of the filling container is 2/3 or more, preferably 4/5 or more, and more preferably 9/10 or more.

The filling container used in the filling method of the present invention has the above-mentioned structure so that the carrier gas circulates in the partitioned space, and the carrier gas is discharged Exit (3).

In the filling container used in the present invention, in the example of the partition wall (1) provided with the aforementioned opening (30), the example in the case where the partition wall (1) is one piece can be as shown in the structure of Fig. 1, In addition, when the partition wall (1) has two pieces, it can be as shown in the structure of Figure 2, and when the partition wall (1) has three pieces, it can be as shown in the structure of Figure 3 or 4 By.

In addition, according to the opening (30) provided in the partition wall (1), in order to allow the carrier gas to pass through the opening (30) from the carrier gas inlet (2), circulate in all spaces, and then circulate to the carrier gas outlet (3) , And can be made into a structure in which the carrier gas inlet (2) and the carrier gas outlet (3) are provided with flow passages (31) respectively. As an example of a filling container having a structure having a flow path (31) provided at the carrier gas inlet (2) and the carrier gas outlet (3), the structure shown in Figs. 7 and 8 can be used.

The above-mentioned flow passage (31) can be used: for example, a tubular shape as shown in Figure 9, or a flow passage lower opening at the lower part of the structure partitioned by the partition wall (1) shown in Figures 10 and 11 (32) person. The aforementioned flow passage (31) may be a combination of these tubular ones or those having a flow passage lower opening (32) at the lower part of the structure partitioned by the partition wall (1).

The position of the lower opening (32) of the flow passage (31) of the flow passage (31) is set at 1/3 or less of the inner bottom surface of the filling container, ideally 1/5 or less, and more desirably 1/ Position below 10 .

Based on Fig. 1, the flow form of the carrier gas in the filling container used in the filling method of the present invention will be explained. First, the carrier gas is introduced from the carrier gas inlet (2) and circulates in the space with the carrier gas inlet (2). The carrier gas circulates in each space through the opening (4), and is discharged from the carrier gas discharge port (3) to be supplied to the MOCVD device. Furthermore, the flow form of the carrier gas will be explained based on Figure 1. However, as shown in Figures 2 to 4, when the filling container is divided into 3 or more spaces, the carrier gas is provided in each partition wall. The opening part (30) of (1) circulates.

For this flow pattern, the carrier gas inlet (2) and the carrier gas discharge port (3) are provided with flow channels (31) as shown in Figure 7, and the carrier gas is introduced through the carrier gas inlet (2). After circulating in the flow passage (31), it then circulates in the space with the carrier gas inlet (2). The carrier gas circulates in each space through the opening (30), then circulates through the flow path (31) provided in the carrier gas discharge port (3), and is discharged from the carrier gas discharge port (3) to be supplied to the MOCVD device.

In addition, for the filling container for solid organometallic compound used in the filling method of the present invention, a filling port for filling the solid organometallic compound can be provided in the space inside the filling container formed by the partition (1). (9). By providing this filling port (9), the solid organometallic compound can be directly injected in a solid state. In the present invention, the filling port of the filling container can be provided on the upper part of the filling container as shown in FIGS. 1 to 4. In addition, by making the carrier gas introduction port (2) and/or bearing The carrier gas outlet (3) can be separated from the filling container, and it can be configured to use both the carrier gas inlet (2) and/or the carrier gas outlet (3) and the filling port (9). The separated carrier gas inlet (2) and/or carrier gas outlet (3) and the filling container can be used after being joined again via the connecting member. As an example of this structure, as shown in Figure 12, a separable connection part (26) is provided as a filling port between the carrier gas inlet (2) and the filling container, and the connection part (26) ) User after rejoining.

Furthermore, in the filling container used in the filling method of the present invention, for example, as shown in Figures 1 to 4, the carrier gas inlet (2) and the carrier gas outlet (3) can be provided with switchable valves ( 22) When the carrier gas is circulating, the valve (22) is opened for use. In addition, when the organometallic compound is not supplied, the valve is usually closed to prevent the solid organometallic compound from being externally contaminated or facing the filling container. The external sublimation and evapotranspiration.

In this way, the structure of the filling container used in the filling method of the present invention is that 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 All the spaces in the solid organometallic compound in the container space circulate from the upper part of these spaces through the lower part of the space to the carrier gas discharge port (3). In this way, by dividing the inside of the container with the partition wall (1) and dividing it into a plurality of spaces, the cross-sectional area of each space is reduced, and the contact between the carrier gas and the solid organometallic compound can be sufficiently carried out, so there is no such thing as the conventional technology. The flow path can evenly maintain the contact state of the carrier gas and the solid organometallic compound. With the carrier gas, the container can be filled for a long period of time. The solid organometallic compound is stably supplied to the MOCVD device at a constant concentration. By filling the container with a solid organometallic compound with a controlled particle size and using it, the effect of the particle size control can be further derived.

Moreover, in addition to the filling container for solid organometallic compounds of the aforementioned structure, the filling method of the present invention can be used: for the filling container for solid organometallic compounds having a carrier gas inlet and a carrier gas discharge port, it is characterized by: The inside of the filling container is divided into a plurality of vertical spaces. By means of reversing the direction of the carrier gas flow, the carrier gas introduced from the carrier gas inlet is circulated in each vertical space as a downward counterflow, and the carrier gas is discharged from the outlet. Expelled.

The aforementioned filling container that can be used in the present invention is not particularly limited in its structure as long as the internal space is divided into a plurality of vertical spaces and the carrier gas is circulated in each vertical space as a downward countercurrent flow.

The means for reversing the flow direction of the carrier gas of the present invention is used to reverse the flow direction of the carrier gas circulating in the divided space as a downward countercurrent flow, and supply it as a downward countercurrent flow above the adjacent vertical space The means. Specific examples of the means for reversing the flow direction of the carrier gas include: as shown in Figures 13-20, a connecting flow path is provided in the partition wall; as shown in FIGS. 21 and 22, the connecting flow path constitutes the partition wall; or As shown in Figs. 23 and 24, the connecting flow passages are formed by partitions, but it is not limited to these.

Figures 13 to 16 show an example of a filling container for a solid organometallic compound used in the present invention. As shown in Figures 13 to 16, the filling container for solid organometallic compounds used in the filling method of the present invention has: at least one partition wall (1) separates the filling container in the longitudinal direction. The inside of the device is divided into at least two spaces. The partition method of the space according to the partition (1) is, for example, a structure that partitions the space as shown in Figures 1 to 4.

The outer shape of the filling container can be made into a cylindrical container as shown in Figures 13-16, but can also be made into a triangular column, a quadrangular column, a pentagonal column, a hexagonal column, and the like.

In addition, the structure of the filling container for solid organometallic compounds used in the filling method of the present invention has a carrier gas inlet (2) communicating with one of the spaces in the filling container formed by partitioning (1) ), and has a carrier gas discharge port (3) connected to one of the remaining spaces. For example, the structure shown in Figs. 13-16 can be cited. The carrier gas is introduced into the filling container filled with the solid organometallic compound from the carrier gas inlet (2), so that it circulates inside the filling container, and the carrier gas outlet (3) uses the organometallic compound as saturated in the carrier gas The gas is taken out and supplied to the MOCVD device. The carrier gas inlet (2) and carrier gas outlet (3) are arranged in the filling container according to the partition method of the partition wall (1) or the use form of the filling container. For example, in the filling container The upper part has a structure with a carrier gas inlet (2) and a carrier gas outlet (3), or a structure provided on the side of the filling container.

The partition (1) inside the filling container used in the present invention, as shown in Figs. 13-16, includes: each space provided with a carrier gas for passing the carrier gas through the filling container through the carrier gas inlet (2) Circulates to the lower opening (4) and upper opening (5) of the carrier gas outlet (3) ) Is the next wall (1) of the connecting flow path (6).

In addition, the structure of the filling container of the present invention is as shown in Figures 13-16. The carrier gas introduced into the filling container is introduced through the lower opening (4) of the connecting flow path (6) and discharged to the upper opening (5). ).

Since the filling container of the present invention is provided with the flow passage of the above-mentioned structure, the carrier gas flows through the compartments that have been partitioned, and is discharged from the carrier gas discharge port (3).

In addition, the filling container of the present invention is shown in Figures 13 to 16, including: a carrier gas is discharged from the lower part of the space having the carrier gas discharge port (3) to the lower opening (7) of the carrier gas discharge port (3). ) Of the discharge flow path (8).

In the filling container of the present invention, as an example of the aforementioned connecting flow path (6) and flow path (8), when the partition wall (1) is one piece, for example, the structure shown in Fig. 13 can be used for When there are two partition walls (1), for example, what is shown in the structure of FIG. 14 can be used, and when there are three partition walls (1), it can be, for example, what is shown in the structure of FIG. 15 or 16.

In the filling container for a solid organometallic compound of the present invention, the communication flow path (6) can be provided with one or more pipes as shown in Figs. 17-20.

The flow form of the carrier gas in the filling container of the present invention will be explained based on Fig. 13. First, the carrier gas is introduced from the carrier gas inlet (2) and descends in the space with the carrier gas inlet (2). The carrier gas flows in from the lower opening (4) of the connecting flow channel (6) as a means for reversing the direction of the carrier gas flow located near the bottom of the container, as an upward countercurrent flow It circulates in the connecting flow path (6) and is supplied to the upper part of the space with the carrier gas discharge port (3). The carrier gas supplied to the upper part of the space having the carrier gas discharge port (3) descends. The lower opening (7) of the discharge flow passage (8) located in the lower part of the space with the carrier gas discharge port (3) rises in the discharge flow passage (8) and is discharged from the carrier gas discharge port (3) to Supplied to the MOCVD device. Furthermore, the flow form of the carrier gas will be explained based on Fig. 13, but as shown in Figs. 14-16, when the filling container is divided into 3 or more spaces, the carrier gas is provided in each partition ( The connecting flow passage (6) of 1) circulates from above to below as a downward flow in each space.

In addition, as shown in Figures 21 to 24, the same effect can be achieved even if the partition wall (1) also serves as the connecting flow path (6). As these structures, tubular structures can also be made. For example, as shown in Fig. 21, the tubular structures are arranged in the longitudinal direction of the container, and the gaps are blocked in the form of continuous tubular structures; or as shown in Fig. 22 As shown in the figure, the partition wall (1) is made to block the gap of the tubular structure, and further for the direction of the carrier gas flow, an opening is provided in the upper part of the tubular structure on the upstream side of the space side, and this is used as the lower opening (4), The upper part of the space on the downstream side is provided with an opening as the upper opening (5); or as shown in Figure 23 or 24, the partition wall (1) is made into two pieces. For the direction of the carrier gas flow, An opening is provided under the partition wall (1) on the upstream side as the lower opening (4), and an opening is provided above the partition wall (1) on the downstream side as the upper opening. (5) Person. The aforementioned connecting flow path (6) can also be of these tubular structures or The partition wall (1) also serves as a flow path combined with the structure of the connecting flow path (6).

In addition, in the filling container of the present invention, the discharge flow path (8) with a lower opening (7) that discharges the carrier gas from the lower part of the space having the carrier gas discharge port (3) to the carrier gas discharge port (3) ), for example, a tubular structure having an opening at the lower part as shown in Fig. 25, or a tubular structure having an opening at the lower part as shown in Fig. 25, or as shown in Fig. 26 or 27, having a lower opening part ( 7) Those who wait. The aforementioned discharge flow passage (8) may be a combination of these tubular structures or a flow passage having a lower opening (7) at the lower part of the structure partitioned by the partition wall (1).

In addition, the filling container for solid organometallic compounds of the present invention aims at the communication flow path (6) having the lower opening (4) and the upper opening (5) for circulating each carrier gas and the carrier gas discharge port. The lower part of the space (3) has a discharge flow path (8) with a lower opening (7) for discharging the carrier gas toward the carrier gas discharge port (3), these upper openings (5) and lower openings (4) If the carrier gas can pass through the space filled with solid organometallic compound or the connecting flow path (6) and the discharge flow path (8) with the lower opening (7) to the carrier gas discharge port (3) , The carrier gas inlet (2) can fully circulate toward the carrier gas outlet (3). At this time, the filled solid organometallic compound can fully contact the carrier gas, which will not cause the stable supply of the organometallic compound. The position of the hindrance is not particularly limited, but especially in order to effectively saturate the filled solid organometallic compound with the carrier gas, it is used to circulate the carrier gas. The connecting flow path (6) of the lower opening (4) and the upper opening (5) of the filling container, the lower opening (4) should be set at 1/3 or less of the inner height of the container from the inner bottom surface of the filling container, which is ideal It is 1/5 or less, more preferably 1/10 or less, and the upper opening (5) is set at 2/3 or more, ideally 4/5 or more, of the internal bottom surface of the filling container. More desirably, the position above 9/10 is that the carrier gas is discharged from the lower part of the space with the carrier gas discharge port (3) to the discharge flow path ( 8) It is desirable that the lower opening (7) is provided at a position of 1/3 or less, ideally 1/5 or less, and more desirably 1/10 or less of the internal height of the container from the inner bottom surface of the filling container.

When the solid organometallic compound is filled in the filling container of the present invention to supply the organometallic compound to the MOCVD device, the space inside the filling container is filled with the solid organometallic compound.

Furthermore, in the filling container for solid organometallic compound of the present invention, a filling port (9) for filling the solid organometallic compound can be provided in the space inside the filling container formed by the partition (1). By providing this filling port (9), the solid organometallic compound can be directly injected in a solid state. In the present invention, the filling port of the filling container can be provided on the upper part of the filling container as shown in FIGS. 13-16. In addition, by creating a structure in which the carrier gas inlet (2) and/or the carrier gas outlet (3) can be separated by the filling container, it is possible to make the carrier gas inlet (2) and/or the carrier gas outlet (3) ) And the structure of the filling port (9). The separated carrier gas inlet (2) and/or carrier gas The discharge port (3) and the filling container can be used after being joined again via the connecting member. At this time, the flow path (8) connected to the carrier gas discharge port (3) is also made into a separable structure, making it easy to fill the solid organometallic compound. As an example of this structure, as shown in Figure 28, a separable connecting part (26) is provided as a filling port between the carrier gas inlet (2) and the filling container, and the connecting part (26) ) User after rejoining.

Furthermore, in the filling container used in the filling method of the present invention, for example, as shown in Figures 13-16, a switchable valve ( 22). When the carrier gas is circulating, the valve (22) is opened for use. In addition, when the organometallic compound is not supplied, the valve is usually closed to prevent the solid organometallic compound from being externally contaminated or facing the filling container. The external sublimation and evapotranspiration.

In this way, the structure of the filling container used in the filling method of the present invention is that 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 All the spaces in the solid organometallic compound in the container space circulate from the upper part of these spaces through the lower part of the space to the carrier gas discharge port (3). In this way, by dividing the inside of the container with the partition wall (1) and dividing it into a plurality of spaces, the cross-sectional area of each space is reduced, and the contact between the carrier gas and the solid organometallic compound can be sufficiently carried out, so there is no such thing as the conventional technology. The flow path can evenly maintain the contact state of the carrier gas and the solid organometallic compound. With the carrier gas, the container can be filled for a long period of time. The solid organometallic compound is stably supplied to the MOCVD device at a constant concentration. By filling the container with a solid organometallic compound with a controlled particle size and using it, the effect of the particle size control can be further derived.

With the solid organometallic compound filling method of the solid organometallic compound filling container of the present invention, the solid organometallic compound is filled into the filling container and used when the supply of the organometallic compound is supplied to the MOCVD device. The internal space is filled with solid organometallic compounds.

The filling method of the solid organometallic compound in the filling container for solid organometallic compound of the present invention, as a method of filling the solid organometallic compound into the space inside the filling container, can directly use the well-known method, for example, Use: a method of introducing a solid organometallic compound into a filling container by sublimation, or, for example, a method of introducing an organometallic compound as a saturated vapor in a carrier gas into the filling container, or, for example, heating the organometallic compound to melt There are several methods such as making it into a liquid state and introducing it into a filling container. However, many of these methods have a case where it is difficult to control the particle size of the solid organometallic compound.

Generally, in the filling of the solid organometallic compound with the particle size controlled in the present invention, the filling container for the solid organometallic compound does not require special operations as described above, and the space provided in the filling container is used for In the filling container filled with the filling port of the solid organometallic compound, the solid organometallic compound with controlled particle size can be directly injected in the solid state from the outside of the filling container.

This solid organometallic compound is, for example, a substance that ignites in the air In this case, solid organometallic compounds such as nitrogen, argon, helium, etc. can be filled from the filling port of the aforementioned solid organometallic compound under an inert gas environment.

For the solid organometallic compound that can be used for filling in the filling container of the present invention, not only the solid organometallic compound used in the well-known filling container, but also other solid organometallic compounds can be used. Supply temperature of carrier gas. The pressure is also suitable for the carrier gas that can reach the saturated vapor pressure of the desired supply and is solid under the supply conditions. Representative examples of these solid organometallic compounds include alkyl metal compounds, aromatic ring olefin metal compounds, β-diketone coordination compounds, and addition compounds. Specifically, for example, trimethylindium, trimethylindium, and trimethylindium can be mentioned. Alkyl metal compounds such as methyl indium chloride, triphenyl aluminum, triphenyl bismuth, tert-butyl lithium, etc.; cyclopentadienyl indium, dicyclopentadienyl magnesium, dicyclopentadienyl manganese, dicyclopentadienyl manganese, etc. Aromatic cycloalkene metal compounds such as ferrocene; barium acetylacetonate coordination compounds, strontium acetone acetone coordination compounds, copper acetone acetone coordination compounds, calcium acetone acetone coordination compounds, trimethyl acetone sheep copper (di- β-diketone coordination compounds such as pivaloyl methanate Cu coordination compounds, di-pivaloyl methanate Y coordination compounds, and di-pivaloyl methanate Ca coordination compounds; three Methyl indium. Trimethylarsine addition compound, trimethylindium. Trimethylphosphine addition compound, ethyl Barium acetone. 1, 10-phenanthroline addition compound and other addition compounds.

In addition, the pressure at the time of using the filling container filled with the solid organometallic compound by the method of the present invention does not need to change the filling which is well known so far. The conditions used for the filling container are used. If the conditions can be used to supply the solid organometallic compound to the MOCVD device stably for a long period of time, it is not particularly limited. It can be used under pressure, normal pressure, and reduced pressure, but usually Use under reduced pressure near normal pressure.

In addition, regarding the temperature when using the filling container filled with the solid organometallic compound by the method of the present invention, it can be applied without changing the conditions used in the filling container that is well-known so far. The solid organic compound generally used The metal compound can be applied under the condition that the saturated vapor pressure that can achieve the desired supply for the carrier gas can be obtained and the individual can be formed under the supply conditions.

In the filling container filled with a solid organometallic compound by the filling method of the present invention, the carrier gas can also be used by all the users of the filling container known to the present, for example, nitrogen, argon, helium inactive gas or hydrogen can be used. Wait.

In addition, in the filling container filled with a solid organometallic compound by the filling method of the present invention, a conventional filling material that is filled and used with a solid organometallic compound can be used in a filling container known to the present. As the material for this filler, stainless steel, glass, ceramics, fluororesin, etc. can be used, and it is desirable to use stainless steel. In addition, as the shape of the filling material, various shapes such as circular, angular, cylindrical, coiled, spiral, spherical, etc. can be used. For example, as these examples, various pads for distillation, such as Dick, can be used. Mori liner, spiral liner, Finsky liner, etc. Fibrous fillers can also be used.

In the present invention, as the size of the filler, it can be made by having The size of the opening of the filling port of the filling container is usually 0.8-8 mm, ideally 0.8-6 mm, and more ideally 0.8-5 mm.

These filling materials can be used in the filling container of the present invention together with the solid organometallic compound filled in the filling container by a well-known method.

Furthermore, the filling method of the present invention is not limited to solid organometallic compounds, but can also be transferred to other general solid materials such as solid inorganic compounds, solid organic compounds or solid metals with vapor pressure. In this way, the filling method of the present invention can be used as a filling method for using the carrier gas, replacing the solid organometallic compound with other solid substances, and taking out the gas saturated in the carrier gas.

Hereinafter, the present invention will be described in more detail based on examples.

[Example 1]

Trimethylindium is used as the solid organometallic compound.

Trimethylindium is pulverized in a nitrogen atmosphere, and the particle size of the trimethylindium is made into particles of 4.75 mm or less using a sieve with a 4.75 mm mesh. Then, from the trimethyl indium particles with a particle size of 4.75 mm or less that passed through the sieve, using a sieve with a 1 mm mesh, remove the trimethyl indium particles with a particle size of 1 mm or less, and adjust it to have a particle size of 4.75 mm or less The particle size of trimethyl indium.

Confirm that the particle size of the trimethylindium particles is more than 50% in the size of 2.5~4.75 mm.

Using the thus obtained trimethylindium containing particles with a particle size of 2.5 to 4.75 mm, a supply stability test was performed.

The supply stability test was performed in the following method.

In a nitrogen atmosphere, in a filling container made of SUS with an outer diameter of 60.5 mm φ as shown in Fig. 28, the filling port (9) is filled with 200 g of trimethyl indium whose particle size is controlled by the method described above, 0.9 mm×1.8 263g of stainless steel filler of mm×1.8 mm and 97g of stainless steel filler of 2.5 mm×5.0 mm×5.0 mm. In this filling operation, part of the connecting part (26) is cut away, and the space is used as a filling port (9) for filling.

Next, connect the carrier gas outlet (3) to a trap cooled with dry ice methanol for trapping trimethylindium. Heat the pipe connecting the carrier gas outlet (3) and the trap cooled with dry ice methanol, so that trimethylindium will not precipitate in the pipe. The filling container filled with trimethylindium and the filler is installed in a constant temperature bath at 25°C, and the pressure in the system for the stability test is set to near atmospheric pressure, and the carrier gas inlet of the filling container (2) 500 cc of nitrogen gas was circulated every minute, and the weight of trimethylindium captured by the trap cooled by dry ice methanol was measured every 8 hours. In addition, the gas concentration of the gas phase of the carrier gas containing the vapor of trimethylindium was measured with an ultrasonic concentration agent (trade name: Jebison; manufactured by Thomas Swann).

The result is shown in Figure 29. The vertical axis of the graph shown in Fig. 29 shows the supply amount of trimethylindium per hour, and the horizontal axis shows the use ratio of supplied trimethylindium in wt%.

Provide stability test results, when using the filling method of the present invention In this case, the supply rate of trimethylindium is stable up to 91% by weight of the usage rate.

In this way, by using the solid organometallic compound whose particle size includes particles with a particle size of 2.5 to 4.75 mm, the solid organometallic compound can be supplied stably at a certain concentration, and under the condition that a stable supply rate is obtained , Can increase the use ratio of solid organometallic compounds. As a result, it is possible to increase the period during which the solid organometallic compound is stably supplied.

[Comparative example]

In Comparative Example 1, except that trimethylindium was pulverized in a nitrogen atmosphere, and a sieve with a 2.36 mm mesh was used to make trimethylindium into particles with a particle size of 2.36 mm or less, the rest was the same as in Example 1. The same operation is used to test the supply stability of the solid organometallic compound. The result is shown in Figure 30. On the vertical axis of the graph shown in Fig. 30, the supply amount of trimethylindium per hour is shown, and on the horizontal axis, the use ratio of the supplied trimethylindium is shown in weight %. As a result of the test of supply stability, the supply rate of trimethylindium, which does not include particles with a particle size of 2.5-6 mm, is stable until the usage rate is 77% by weight.

In this way, when using trimethylindium that does not contain trimethylindium particles with a particle size of 2.5-6 mm, it is impossible to obtain a stable supply rate for a long period of time as shown in Example 1.

[Example 2]

In Example 2, in addition to using the filling container as a SUS filling container with an outer diameter of 76 mm φ as shown in Fig. 28, a controlled particle size of 400 g trimethyl indium, 0.9 mm×1.8 mm×1.8 mm was used. Except for 394 g of the stainless steel filler and 78 g of the 2.5 mm×5.0 mm×5.0 mm stainless steel filler, the same operation as in Example 1 was performed to test the supply stability of the solid organometallic compound. The result is shown in Figure 31. The vertical axis of the graph shown in Fig. 31 shows the supply amount of trimethyl indium per hour, and the horizontal axis shows the use ratio of supplied trimethyl indium in wt%. As a result of the supply stability test, the supply rate of trimethylindium containing particles with a particle size of 2.5-6 mm was stable until the usage rate was 85% by weight.

[Example 3]

In Example 3, in addition to the filling container having the structure shown in Figure 34 except for the diffuser (20a), a glass filling container with an outer diameter of 35 mm φ was used. Except for 100 g of methyl indium, the same operation as in Example 1 was performed to test the supply stability of the solid organometallic compound. As a result of the supply stability test, the supply rate of trimethylindium containing particles with a particle size of 2.8 to 4.75 mm was stable until the usage rate was 76% by weight.

[Comparative Example 2]

In Comparative Example 2, in addition to pulverizing trimethylindium in a nitrogen atmosphere, a sieve with a mesh opening of 2.36 mm was used to make trimethylindium to have a particle size of 2.36 Except for particles below mm, the same operations as in Example 1 were performed to test the supply stability of the solid organometallic compound. The result is shown in Figure 32. The vertical axis of the graph shown in Fig. 32 shows the supply amount of trimethylindium per hour, and the horizontal axis shows the usage rate of supplied trimethylindium in wt%. As a result of the test of supply stability, the supply rate of trimethylindium, which does not include particles with a particle size of 2.5-6 mm, is stable up to 59% by weight of the usage rate.

As such, when the trimethylindium, which is an example that does not contain trimethylindium with a particle size of 2.5-6 mm, is filled and used, it is impossible to obtain a stable supply rate for a long period of time as in Example 2.

[Comparative Example 3]

In Comparative Example 3, except that trimethylindium was pulverized in a nitrogen atmosphere and trimethylindium was made into particles with a particle size of 0.1-0.3 mm or less, the same operations as in Example 3 were performed to test the solid organic Supply stability of metal compounds. As a result of the test of supply stability, the supply rate of trimethylindium with a particle size of 0.1~0.3 mm is stable until the usage rate is 20% by weight.

As such, when trimethylindium with a particle size of 0.1 to 0.3 mm is filled and used, it is impossible to obtain a stable supply rate for a long period of time as in Example 3.

Industrial use possibilities

According to the present invention, when the solid organometallic compound is filled in the solid When filling containers for organometallic compounds, the particle size of the solid organometallic compound must contain particles of a certain size. This not only ensures the initial stability, but also enables stable supply of the solid organometallic compound to the MOCVD device for a long period of time. A device for vapor phase epitaxy growth.

<p>1Next door</p><p>2Carrier gas inlet</p><p>3Carrier gas outlet</p><p>4Lower opening</p><p>5Upper opening</p><p>6Connecting flow path</p><p>7Lower opening</p><p>8(For discharge) flow path</p><p>9Filling port</p><p>22Valve</p><p>26Connecting parts</p><p>2aCarrier gas inlet</p><p>3aCarrier gas outlet</p><p>20aDiffuser</p><p>21aSolid organometallic compound configuration room</p><p>22avalve</p><p>23Cylinder container</p><p>24aFilter</p><p>25aEnter the room</p><p>27aPorous component</p>

Fig. 1 is a schematic diagram showing an embodiment of the filling container of the present invention, (A) is a cross-sectional view, (B) is a plan view, and (C) is an oblique view.

Fig. 2 is a schematic diagram showing an embodiment of the filling container of the present invention, (A) is a cross-sectional view, and (B) is a plan view.

Fig. 3 is a schematic diagram showing an embodiment of the filling container of the present invention, (A) is a cross-sectional view, and (B) is a plan view.

Fig. 4 is a schematic diagram showing an embodiment of the filling container of the present invention, (A) is a cross-sectional view, and (B) is a plan view.

Fig. 5 is a schematic diagram showing an embodiment of the filling container of the present invention, (A) is an oblique view, and (B) is a cross-sectional view.

Fig. 6 is a schematic diagram showing an embodiment of the filling container of the present invention, (A) is an oblique view, and (B) is a cross-sectional view.

Fig. 7 is a schematic diagram showing an embodiment of the filling container of the present invention, (A) is a cross-sectional view, (B) is a plan view, and (C) is an oblique view.

Fig. 8 is a schematic diagram showing an embodiment of the filling container of the present invention, (A) is a cross-sectional view, (B) is a plan view, and (C) is an oblique view.

Fig. 9 is a schematic diagram showing an embodiment of the filling container of the present invention, (A) is an oblique view, and (B) is a cross-sectional view.

Fig. 10 is a schematic diagram showing an embodiment of the filling container of the present invention, (A) is an oblique view, and (B) is a cross-sectional view.

Fig. 11 is a schematic diagram showing an embodiment of the filling container of the present invention, (A) is an oblique view, and (B) is a cross-sectional view.

Fig. 12 is a schematic diagram showing an embodiment of the filling container of the present invention, (A) is a cross-sectional view, (B) is a plan view, and (C) is an oblique view.

Figure 13 is a schematic diagram showing an embodiment of the filling container of the present invention, (A) is a cross-sectional view, (B) is a plan view, and (C) is an oblique view.

Fig. 14 is a schematic diagram showing an embodiment of the filling container of the present invention, (A) is a cross-sectional view, and (B) is a plan view.

Fig. 15 is a schematic diagram showing an embodiment of the filling container of the present invention, (A) is a cross-sectional view, and (B) is a plan view.

Fig. 16 is a schematic diagram showing an embodiment of the filling container of the present invention, (A) is a cross-sectional view, and (B) is a plan view.

Fig. 17 is a perspective view showing an embodiment of the present invention.

Fig. 18 is a perspective view showing an embodiment of the present invention.

Fig. 19 is a perspective view showing an embodiment of the present invention.

Fig. 20 is a perspective view showing an embodiment of the present invention.

Fig. 21 is a schematic diagram showing an embodiment of the filling container of the present invention, (A) is an oblique view, and (B) is a cross-sectional view.

Figure 22 is a schematic diagram showing an embodiment of the filling container of the present invention, (A) is an oblique view, and (B) is a cross-sectional view.

Fig. 23 is a schematic diagram showing an embodiment of the filling container of the present invention, (A) is an oblique view, and (B) is a cross-sectional view.

Fig. 24 is a schematic diagram showing an embodiment of the filling container of the present invention, (A) is an oblique view, and (B) is a cross-sectional view.

Fig. 25 is a schematic diagram showing an embodiment of the filling container of the present invention, (A) is an oblique view, and (B) is a cross-sectional view.

Fig. 26 is a schematic diagram showing an embodiment of the filling container of the present invention, (A) is an oblique view, and (B) is a cross-sectional view.

Fig. 27 is a schematic diagram showing an embodiment of the filling container of the present invention, (A) is an oblique view, and (B) is a cross-sectional view.

Fig. 28 is a schematic diagram showing the filling container used in Example 1, (A) is a cross-sectional view, (B) is a plan view, and (C) is an oblique view.

Figure 29 is a graph showing the test results of the supply stability of trimethylindium in Example 1 (the relationship between the use ratio of trimethylindium supplied and the supply amount of trimethylindium per hour).

Figure 30 is a graph showing the test results of the supply stability of trimethylindium in Comparative Example 1 (the relationship between the use ratio of trimethylindium supplied and the supply amount of trimethylindium per hour).

Figure 31 is a graph showing the test results of the supply stability of trimethylindium in Example 2 (the relationship between the use ratio of trimethylindium supplied and the supply amount of trimethylindium per hour).

Figure 32 is a test result showing the stability of the supply of trimethyl indium in Comparative Example 2 (the use ratio of supplied trimethyl indium and the ratio of trimethyl indium per hour The relationship between the supply of base indium).

Figure 33 is a schematic cross-sectional view showing a conventional filling container A.

Figure 34 is a schematic cross-sectional view showing a conventional filling container B.

Figure 35 is a schematic cross-sectional view showing a conventional filling container C.

Figure 36 is a schematic cross-sectional view showing a conventional filling container D.