WO2015145907A1

WO2015145907A1 - Organic metal compound-containing gas supply device

Info

Publication number: WO2015145907A1
Application number: PCT/JP2014/084328
Authority: WO
Inventors: 白井　昌志; 千尋長谷川; 浩二竹林; 晋吉冨
Original assignee: 宇部興産株式会社
Priority date: 2014-03-27
Filing date: 2014-12-25
Publication date: 2015-10-01
Also published as: CN106062244A; JP6237882B2; KR20160137961A; JPWO2015145907A1; TW201600629A

Abstract

[Problem] To provide an organic metal compound supply device that can stably supply an organic metal compound-containing gas stably over a long period of time. [Solution] This supply device (1) of an organic metal compound-containing gas is provided with a container (10), a supply unit (13), and a high-specific gravity object. The container (10) comprises an inner space (10a), a carrier gas inlet (10b) and an exhaust port (10c). The inlet (10b) is connected to the bottom of the inner space (10a). The exhaust port (10c) is connected to the top of the inner space (10a). The supply unit (13) is positioned in the inner space (10a). A mixture of organic metal compound-containing particles and a filler material is arranged in the supply unit (13). The high-specific gravity object is arranged in the inner space (10a), above the supply unit (13). The high-specific gravity object has a specific gravity higher than that of the organic metal compound-containing particles.

Description

Organometallic compound-containing gas supply device

The present invention relates to an apparatus for supplying an organometallic compound-containing gas.

Conventionally, a metal organic chemical vapor deposition method (MOCVD method) has been used for the manufacture of compound semiconductor devices. In the organometallic chemical vapor deposition method, a mixed gas of an organometallic compound and a carrier gas is supplied to a chamber. Patent Document 1 describes an apparatus having a container filled with a solid organometallic compound at room temperature as a gas supply apparatus containing an organometallic compound.

JP 2009-127096 A

There is a demand for supplying an organometallic compound-containing gas in a predetermined concentration range from an organometallic compound-containing gas supply device. That is, the organometallic compound-containing gas supply device is required to be able to supply the organometallic compound-containing gas stably over a long period of time.

The main object of the present invention is to provide an organometallic compound supply device capable of stably supplying an organometallic compound-containing gas over a long period of time.

The organometallic compound-containing gas supply device according to the present invention is a device that supplies a gas containing an organometallic compound that is solid at room temperature. An organometallic compound-containing gas supply device according to the present invention includes a container, a supply unit, and a high specific gravity material. The container has an internal space, a carrier gas introduction port, and a discharge port. The introduction port is connected to the lower part of the internal space. The discharge port is connected to the upper part of the internal space. The supply unit is located in the internal space. A mixture of the organometallic compound-containing particles and the filler is disposed in the supply unit. The high specific gravity is disposed on the supply unit in the internal space. The high specific gravity has a higher specific gravity than the organometallic compound-containing particles.

According to the present invention, it is possible to provide an organometallic compound supply apparatus capable of stably supplying an organometallic compound-containing gas over a long period of time.

FIG. 1 is a schematic cross-sectional view of the organometallic compound-containing gas supply device according to the first embodiment. FIG. 2 is a graph schematically showing the concentration of the organometallic compound in the organometallic compound-containing gas when no high specific gravity material is provided. FIG. 3 is a schematic cross-sectional view of the organometallic compound-containing gas supply device according to the second embodiment. FIG. 4 is a schematic cross-sectional view of the organometallic compound-containing gas supply device according to the third embodiment. FIG. 5 is a schematic cross-sectional view of the organometallic compound-containing gas supply device according to the fourth embodiment. FIG. 6 is a schematic cross-sectional view of the organometallic compound-containing gas supply device according to the fifth embodiment. FIG. 7 is a schematic cross-sectional view of an organometallic compound-containing gas supply device according to a sixth embodiment. FIG. 8 is a schematic cross-sectional view of the organometallic compound-containing gas supply device prepared in Experimental Example 1.

Hereinafter, an example of a preferable embodiment in which the present invention is implemented will be described. However, the following embodiment is merely an example. The present invention is not limited to the following embodiments.

In each drawing referred to in the embodiment and the like, members having substantially the same function are referred to by the same reference numerals. The drawings referred to in the embodiments and the like are schematically described. A ratio of dimensions of an object drawn in a drawing may be different from a ratio of dimensions of an actual object. The dimensional ratio of the object may be different between the drawings. The specific dimensional ratio of the object should be determined in consideration of the following description.

(First embodiment)
FIG. 1 is a schematic cross-sectional view of the organometallic compound-containing gas supply device according to the first embodiment. An organometallic compound-containing gas supply apparatus 1 shown in FIG. 1 is an apparatus that supplies a gas containing an organometallic compound that is solid at room temperature. Specifically, a carrier gas is supplied to the supply device 1. The supply device 1 is a device that supplies a mixed gas of a carrier gas and an organometallic compound that is solid at room temperature.

Note that the type of the organometallic compound that is solid at room temperature is not particularly limited. Specific examples of organometallic compounds that are solid at room temperature include, for example, organolithium compounds, organoindium compounds, organozinc compounds, organoaluminum compounds, organogallium compounds, organomagnesium compounds, organobismuth compounds, organomanganese compounds, and organoiron compounds. And organic barium compounds, organic strontium compounds, organic copper compounds, organic calcium compounds, organic yttrium compounds, and organic cobalt compounds. Specific examples of the organic lithium compound include t-butyl lithium. Specific examples of the organic indium compound include trimethylindium, dimethylchloroindium, cyclopentadienylindium, trimethylindium / trimethylarsine adduct, and trimethylindium / trimethylphosphine adduct. Specific examples of the organic zinc compound include ethyl zinc iodide, ethyl cyclopentadienyl zinc, cyclopentadienyl zinc and the like. Specific examples of the organoaluminum compound include methyldichloroaluminum, triphenylaluminum, tris (dimethylamido) aluminum and the like. Specific examples of the organic gallium compound include methyldichlorogallium, dimethylchlorogallium, dimethylbromogallium and the like. Specific examples of the organic magnesium compound include bis (cyclopentadienyl) magnesium and bis (dimethylamido) magnesium. Specific examples of the organic bismuth compound include triphenyl bismuth and the like. Specific examples of the organic manganese compound include bis (cyclopentadienyl) manganese and bis (dimethylamido) manganese. Specific examples of the organic iron compound include ferrocene. Specific examples of the organic barium compound include bis (acetylacetonato) barium, dipivaloylmethanatobarium • 1,10-phenanthroline adduct, and the like. Specific examples of the organic strontium compound include bis (acetylacetonato) strontium, dipivaloylmethanatostrontium, and the like. Specific examples of the organic copper compound include bis (acetylacetonato) copper, dipivaloylmethanatocopper, and the like. Specific examples of the organic calcium compound include bis (acetylacetonato) calcium and dipivaloylmethanatocalcium. Specific examples of the organic yttrium compound include dipivaloylmethanatoribium and the like. Specific examples of the organic cobalt compound include bis (dimethylamido) cobalt, (t-butylmethylacetylene) (hexacarbonyl) dicobalt, and the like.

The supply device 1 includes a container 10, a supply unit 13, and a high specific gravity material.

The container 10 has an internal space 10a, an introduction port 10b, and a discharge port 10c. The internal space 10a may be columnar, for example. Specifically, the internal space 10a may be, for example, a columnar shape, a prismatic shape, or the like. In the present embodiment, the internal space 10a is cylindrical.

The inlet 10b is connected to the lower part of the internal space 10a. The discharge port 10c is connected to the upper part of the internal space 10a. Accordingly, the carrier gas supplied from the inlet 10b flows in the internal space from the lower side to the upper side and is discharged from the outlet port 10c. Specifically, in the present embodiment, the introduction port 10 b is provided on the bottom wall of the container 10. The discharge port 10 c is provided on the upper wall of the container 10.

The supply unit 13 supplies an organic metal compound gas to the carrier gas. By supplying an organic metal compound gas from the supply unit 13, an organic metal compound-containing gas is generated.

The supply unit 13 is located in the internal space 10a. The internal space 10a includes a first region 10a1 and a second region 10a2 located on the first region 10a1. The supply unit 13 is disposed in the first region 10a1. The volume of the first region 10a1 in which the supply unit 13 is disposed is preferably 20% to 80% of the volume of the internal space 10a.

The supply unit 13 is provided with a mixture of organometallic compound-containing particles and filler.

The organometallic compound-containing particles may be particles composed of an organometallic compound, or may be particles having a carrier and an organometallic compound supported on the carrier. The carrier can be composed of, for example, inorganic oxide particles, metal particles, resin particles, and the like. The carrier is, for example, alumina, silica, mullite, glassy carbon, graphite, potassium titanate, sponge titanium, quartz, silicon nitride, boron nitride, silicon carbide, stainless steel, aluminum, nickel, titanium, tungsten, fluorinated resin, glass, etc. It can comprise by the particle | grains which consist of.

The specific gravity of the organometallic compound-containing particles is preferably 0.5 g / ml to 3.0 g / ml.

The particle diameter of the organometallic compound-containing particles is preferably 0.01 mm to 10.0 mm, and preferably 0.05 mm to 8.0 mm.

The organometallic compound-containing particles may be spherical or may be an irregular shape such as a pulverized product.

The filler is particles that do not substantially contain an organometallic compound. The filler can be composed of, for example, inorganic oxide particles, metal particles, resin particles, and the like. Fillers include, for example, alumina, silica, mullite, glassy carbon, graphite, potassium titanate, sponge titanium, quartz, silicon nitride, boron nitride, silicon carbide, stainless steel, aluminum, nickel, titanium, tungsten, fluorinated resin, glass It can be constituted by particles made up of and the like.

The shape of the filler is not particularly limited. The filler may be, for example, a spherical shape or may be an irregular shape such as a pulverized product.

The specific gravity of the filler is preferably 1.0 g / ml to 15.0 g / ml, and more preferably 2.0 g / ml to 10.0 g / ml.

The particle diameter of the filler is preferably 0.01 mm to 10.0 mm, and more preferably 0.1 mm to 8.0 mm.

High specific gravity is arranged on the supply unit 13 in the internal space 10a. The high specific gravity is located in a part of the second region 10a2. Specifically, the high specific gravity object is disposed in a part of the second region 10a2 on the lower side in the vertical direction. The high specific gravity is disposed in a portion excluding the upper portion of the second region 10a2. In the present embodiment, the upper part in the vertical direction of the second region 10a2 is a space.

The shape of the high specific gravity is not particularly limited. The high specific gravity material may be, for example, a plate shape or the like, but in the present embodiment is a particle shape. A plurality of high specific gravity materials are provided on the supply unit 13. The plurality of high specific gravity objects are provided in layers on the supply unit 13. The plurality of high specific gravity objects constitute a high specific gravity layer 14 located on the supply unit 13. The high specific gravity layer 14 covers substantially the entire supply unit 13. However, in the present invention, it is not always necessary that a plurality of high specific gravity objects are arranged. For example, a single plate-like high specific gravity object having a plurality of through holes may be disposed on the supply unit 13.

By the way, from the viewpoint of filling a large amount of organometallic compound in the container, it is also conceivable to fill only the particles of the organometallic compound in the container. However, as a result of intensive studies by the present inventors, when only the organometallic compound is filled in the container, the carrier gas containing the organometallic compound at a concentration higher than a predetermined concentration is difficult to be supplied from the discharge port over a long period of time. Was found. The reason is not clear, but the following reasons are possible. That is, it is considered that the sublimation and aggregation of the organometallic compound are repeatedly generated in the internal space. For example, it is considered that the amount of sublimation of the organometallic compound is larger than the amount of aggregation of the organometallic compound in an upstream portion of the internal space through which the carrier gas having a low organometallic compound concentration passes. On the other hand, it is considered that the amount of aggregation of the organometallic compound is larger than the amount of sublimation of the organometallic compound in the downstream portion of the internal space through which the carrier gas having a high organometallic compound concentration passes. For this reason, grain growth of organometallic compound-containing particles may occur in the downstream portion of the internal space. Accordingly, adjacent particles are joined to each other, and a portion having a high ventilation resistance and a portion having a low ventilation resistance may occur in the downstream portion of the internal space. It is conceivable that so-called channeling occurs in which the carrier gas preferentially passes through a portion having a lower ventilation resistance than other portions. When channeling occurs, the organometallic compound located in the vicinity of the portion with low ventilation resistance is preferentially consumed, and the organometallic compound located in the portion with high ventilation resistance is less likely to be consumed. As a result, the consumption of the organometallic compound until the concentration of the organometallic compound in the mixed gas falls below a predetermined concentration may be reduced.

In the organometallic compound-containing gas supply device 1, a mixture of organometallic compound-containing particles and particulate filler is arranged in the internal space 10a. For this reason, there is also a portion in which a filler is interposed between adjacent organometallic compound-containing particles. For this reason, even when the amount of aggregation of the organometallic compound is larger than the amount of sublimation of the organometallic compound, there are few portions where the organometallic compounds are adjacent to each other, which is accompanied by the joining of the organometallic compound-containing particles. The occurrence of channeling is suppressed. Therefore, according to the supply apparatus 1, the consumption of the organometallic compound until the density | concentration of the organometallic compound in mixed gas falls below a predetermined density | concentration can be increased.

From the viewpoint of increasing the consumption of the organometallic compound until the concentration of the organometallic compound in the mixed gas falls below a predetermined concentration, the content of the filler in the supply unit 13 is 20% by volume to 80% by volume. It is preferably 30% by volume to 70% by volume.

In addition, it is more effective to arrange the mixture of the organometallic compound particles and the filler particles when the melting point is high and it is difficult to support the organometallic compound on the carrier. Therefore, organolithium compounds, organoindium compounds, organozinc compounds, organoaluminum compounds, organogallium compounds, organomagnesium compounds, organobismuth compounds, organomanganese compounds, organoiron compounds, organobarium compounds, organostrontium compounds as organometallic compounds The supply device 1 is more useful when using at least one of an organic copper compound, an organic calcium compound, an organic yttrium compound, and an organic cobalt compound.

As a result of further diligent research, the present inventors have found that when a mixture of organometallic compound-containing particles and particulate filler is disposed in the internal space 10a, the organometallic compound-containing gas immediately after the start of the supply of the carrier gas. It was discovered that the concentration of the organometallic compound becomes too high. Specifically, as in the schematic graph shown in FIG. 2, immediately after the start of the supply of the carrier gas, the concentration of the organometallic compound in the organometallic compound-containing gas becomes stable once it suddenly increases. Since the concentration of the organometallic compound is once increased in this way, the concentration of the organometallic compound in the organometallic compound-containing gas is allowed to be an allowable lower limit C1 and the allowable lower limit until the concentration of the organometallic compound is stabilized after the supply of the carrier gas is started. There are cases where it does not fall within the upper limit C2. In addition, since a large amount of the organometallic compound is consumed at the start of the supply of the carrier gas, the period until the concentration of the organometallic compound in the organometallic compound-containing gas falls below the allowable lower limit C1 is shortened. That is, the period T1 in which the concentration of the organometallic compound in the organometallic compound-containing gas is located between the allowable lower limit value C1 and the allowable upper limit value C2 is shortened.

As a result of further intensive studies, the present inventors have found that the cause of the above phenomenon is that at least the upper part of the mixture disposed in the supply unit 13 rises with the carrier gas at the start of the supply of the carrier gas. When at least the upper part of the mixture arranged in the supply unit 13 rises together with the carrier gas, the higher specific gravity of the organometallic compound-containing particles and the filler gathers downward, and the lower specific gravity gathers upward. . Usually, since the specific gravity of the organometallic compound-containing particles is lower than the specific gravity of the filler, the organometallic compound-containing particles gather together. As a result, a layer having a high concentration of the organometallic compound-containing particles is formed. As a result, it is considered that the concentration of the organometallic compound in the organometallic compound-containing gas temporarily increases.

Therefore, in this embodiment, a high specific gravity material having a higher specific gravity than the organometallic compound-containing particles is arranged on the supply unit 13. It is possible to prevent the organometallic compound-containing particles and the filler disposed in the supply unit 13 from rising due to the high specific gravity when the carrier gas starts to be supplied. Therefore, as shown in FIG. 2, it is possible to suppress the concentration of the organometallic compound from exceeding the allowable upper limit C2 at the start of the supply of the carrier gas. Moreover, since excessive consumption of the organometallic compound is unlikely to occur at the start of the supply of the carrier gas, the organometallic compound-containing gas having a concentration equal to or higher than the allowable lower limit C1 can be supplied over a long period. Therefore, the supplyable period T2 of the organic metal compound-containing gas having a concentration located between the allowable lower limit value C1 and the allowable upper limit value C2 can be lengthened.

From the viewpoint of extending the period during which the organometallic compound-containing gas having a predetermined concentration can be supplied, it is preferable to arrange a high specific gravity so as to cover the supply unit 13. From this viewpoint, it is preferable that the high specific gravity layer 14 including a plurality of high specific gravity materials is provided on the supply unit 13.

The specific gravity of the high specific gravity material is preferably 1.01 times or more, more preferably 1.10 times or more of the specific gravity of the organometallic compound-containing particles.

Hereinafter, another example of the preferred embodiment of the present invention will be described. In the following description, members having substantially the same functions as those of the first embodiment are referred to by the same reference numerals, and description thereof is omitted.

(Second Embodiment)
FIG. 3 is a schematic cross-sectional view of the organometallic compound-containing gas supply device 1a according to the second embodiment. As shown in FIG. 3, in this embodiment, the high specific gravity layer 14 includes a first high specific gravity layer 14a and a second high specific gravity layer 14b. The second high specific gravity layer 14b is located on the first high specific gravity layer 14a. The specific gravity of the second high specific gravity material arranged in the second high specific gravity material layer 14b is higher than the specific gravity of the first high specific gravity material arranged in the first high specific gravity material layer 14a. As described above, by providing the second high specific gravity layer 14b including a high specific gravity material having a higher specific gravity, the scattering of the organometallic compound-containing particles and the filler at the start of the supply of the carrier gas is more effectively suppressed. be able to.

In the present embodiment, the example in which the second high specific gravity material is arranged on the first high specific gravity material has been described. However, the present invention is not limited to this configuration. The first high specific gravity product and the second high specific gravity product may be mixed and arranged.

(Third embodiment)
FIG. 4 is a schematic cross-sectional view of the organometallic compound-containing gas supply device 1b according to the third embodiment. As shown in FIG. 4, in the supply apparatus 1b, the diffusion layer 15 is disposed below the supply unit 13 (on the introduction port 10b side) in the internal space 10a. By providing the diffusion layer 15, the carrier gas can be uniformly supplied to the entire supply unit 13. In addition, the diffusion layer 15 can be comprised with a filler, for example.

(Fourth embodiment)
FIG. 5 is a schematic cross-sectional view of the organometallic compound-containing gas supply device 1c according to the fourth embodiment.

In the first to third embodiments, the example in which the organometallic compound-containing gas supply device has only one container 10 has been described. However, the present invention is not limited to this configuration. For example, as illustrated in FIG. 5, the supply device 1 c includes a container 20 in addition to the container 10. The container 20 is connected to the container 10 in series. Specifically, the discharge port 20 c connected to the internal space 20 a of the container 20 is connected to the introduction port 10 b of the container 10. The carrier gas inlet 20 b of the container 20 is provided at the upper part of the container 20, and the outlet 20 c is provided at the lower part of the container 20. For this reason, in the container 20, the carrier gas flows downward from above.

The supply unit 23 is substantially the same as the supply unit 13. In the supply unit 23, organometallic compound-containing particles and a filler are arranged.

Below the supply unit 23, a filler layer 21 in which a filler is disposed is provided.

By the way, an organometallic compound-containing gas supply device is required to be able to supply an organometallic compound-containing gas stably over a long period of time. That is, it is preferable that a carrier gas containing an organometallic compound at a concentration equal to or higher than a predetermined concentration is supplied from a discharge port over a long period of time. In order to realize this, it is important to increase the consumption of the organometallic compound until the concentration of the organometallic compound in the mixed gas falls below a predetermined concentration.
The reason why the consumption of the organometallic compound is reduced until the concentration of the organometallic compound in the mixed gas falls below a predetermined concentration is that the portion of the container filled with the organometallic compound has the airflow resistance of the carrier gas at the other portion. It is conceivable that so-called channeling occurs in which a lower portion is generated and the carrier gas preferentially passes through a portion in which the carrier gas ventilation resistance is low. When channeling occurs, the organometallic compound located in the vicinity of the portion with low ventilation resistance is preferentially consumed, and the organometallic compound located in the portion with high ventilation resistance is less likely to be consumed. As a result, the consumption of the organometallic compound until the concentration of the organometallic compound in the mixed gas falls below a predetermined concentration may be reduced.
In the supply device 1c, when 60% or more of the organometallic compound in the container 20 is consumed, the carrier gas ventilation resistance in the entire filler layer 21 is higher than the carrier gas ventilation resistance in the entire supply unit 23. As described above, the filler layer 21 is filled with the filler. For this reason, when 60% or more of the organometallic compound in the container 20 is consumed, the filler layer 21 having a relatively high carrier gas ventilation resistance is present, whereby the carrier gas ventilation resistance is provided in the supply unit 23. However, it is difficult to generate a lower part than other parts. Accordingly, the carrier gas passes through the supply unit 23 with high uniformity. As a result, it is possible to increase the amount of consumption of the organometallic compound until the concentration of the organometallic compound in the mixed gas falls below a predetermined concentration. That is, according to the supply apparatus 1, the carrier gas containing the organometallic compound at a concentration equal to or higher than a predetermined concentration can be supplied from the discharge port over a long period of time.

Specifically, when 60% or more of the organometallic compound in the container 20 is consumed, the carrier gas ventilation resistance in the entire filler layer 21 is higher than the carrier gas ventilation resistance in the entire supply unit 23. As such a method, for example, when 60% or more of the organometallic compound in the container 20 is consumed, a method in which the porosity in the filler layer 21 is lower than the porosity in the supply unit 23 is conceivable. . As an example of a method for realizing this, it is conceivable that the average particle diameter of the filler filled in the filler layer 21 is equal to or smaller than the average particle diameter of the carrier of the carrier filled in the supply unit 23. Similarly, when the supply unit 23 is filled with a mixture of a filler and an organometallic compound, the average particle diameter of the filler filled in the filler layer 21 is similarly set to the average particle of the filler in the supply unit 13. It can be considered that the diameter is equal to or smaller than the diameter.

The ratio of the amount of the organometallic compound remaining in the container 20 to the amount of the organometallic compound in the container 20 before use of the supply device 1c ((the amount of the organometallic compound remaining in the container 20) / (supply When the amount of the organometallic compound in the container 20 before use of the apparatus 1c) is 40% or less, the carrier gas ventilation resistance in the entire filler layer 21 is more than the carrier gas ventilation resistance in the entire supply unit 23. It is only necessary that the filler layer 21 is filled with a filler so as to be high. For example, when ((amount of organometallic compound remaining in the container 20) / (amount of organometallic compound in the container 20 before using the supply apparatus 1c)) is 40% or less, it is larger than 40%. Sometimes, the filler layer 21 may be filled with a filler so that the carrier gas ventilation resistance in the entire filler layer 21 is higher than the carrier gas ventilation resistance in the entire supply unit 23.

In the present embodiment, the portion of the internal space 20a on the discharge port 20c side is tapered toward the discharge port 20c side. Specifically, the end of the supply unit 23 on the filler layer 21 side and the filler layer 21 are tapered toward the discharge port 20c as a whole. For this reason, it is possible to prevent the carrier gas from being biased and supplied to a part of the supply unit 23, and a uniform carrier gas can be supplied to the entire supply unit 23. As a result, the amount of consumption of the organometallic compound until the concentration of the organometallic compound in the mixed gas falls below a predetermined concentration can be increased.
(Experimental example 1)
In Experimental Example 1, the organometallic compound-containing gas supply device shown in FIG. 8 was produced under the following conditions.
Container 20:
Taper at the lower end of the internal space: 10.1cc
A cylindrical portion excluding the tapered portion at the lower end of the internal space: 182.4 cc
21 cc of alumina spheres with a diameter of 0.5 mm are placed at the bottom of the internal space, and a mixture of 24.9 g (48 cc) of Cp2Mg and 42 cc of alumina spheres with a diameter of 0.5 mm is placed on it. Were provided with 86 cc of alumina spheres having a diameter of 0.5 mm.
Container 10:
A 1.1 cc tapered portion that thickens upward at the lower end of the inner space A cylindrical portion excluding the tapered portion of the inner space: 18.8 cc
A mixture of 1.90 g (4 cc) of Cp2Mg and 10.7 cc of alumina spheres having a diameter of 0.5 mm was disposed at the bottom of the internal space, and 8 cc of alumina spheres having a diameter of 0.5 mm were disposed thereon.
(Experimental example 2)
A mixture of Cp2Mg 24.61 g (50 cc) and an alumina sphere 44 cc having a diameter of 0.5 mm was disposed at the lowermost part of the internal space of the container 20, and an alumina sphere 109 cc having a diameter of 0.5 mm was disposed thereon. . A mixture of 1.65 g (3.7 cc) of Cp2Mg and 12.2 cc of alumina spheres having a diameter of 0.5 mm is disposed at the lowermost part of the internal space of the container 10, and an alumina sphere having a diameter of 0.5 mm is disposed thereon. 9cc was distributed. Otherwise, an organometallic compound-containing gas supply device was produced under the same conditions as in Experimental Example 1.
(Evaluation)
Argon gas was supplied as a carrier gas at 2000 ccm to the organometallic compound-containing gas supply device produced in each of Experimental Example 1 and Experimental Example 2 under the conditions of 60 ° C. and 760 Torr. At that time, the amount of Cp2Mg extracted per unit time (removal speed) in the gas supplied from the supply device was measured. The ratio of the amount of Cp2Mg taken out until the takeout speed becomes 5% of the takeout speed at the beginning of use with respect to the charged amount of Cp2Mg (until the takeout speed becomes 5% of the takeout speed at the beginning of use) The amount of Cp2Mg taken out in (3) / the amount of Cp2Mg charged) was determined as the stable end point (%). As a result, in Experimental Example 2, the stable extraction end point was about 75%, whereas in Experimental Example 1, the stable extraction end point was about 95%.

(Fifth embodiment)
FIG. 6 is a schematic cross-sectional view of the organometallic compound-containing gas supply device 1d according to the fifth embodiment.
From the viewpoint of filling a larger amount of the organometallic compound in the container, it is preferable to fill the tapered second portion with the organometallic compound. However, as a result of intensive studies, the inventors have found that when the tapered second portion is filled with an organometallic compound, the organometallic compound-containing gas cannot be stably supplied over a long period of time. That is, the present inventors have found that when the tapered second portion is filled with the organometallic compound, the carrier gas containing the organometallic compound at a concentration equal to or higher than a predetermined concentration cannot be supplied from the discharge port over a long period of time. .
The cause of this is not clear, but the flow rate of the carrier gas in the portion near the side wall of the tapered second portion is smaller than the flow rate of the carrier gas in the other portions. This is considered to be because the utilization efficiency of the organometallic compound disposed in the vicinity of the side wall of the metal decreases.
Therefore, as shown in FIG. 6, in the supply device 1d, in addition to the tapered portion of the internal space 20a, the filler layer 21 is located above the tapered portion. For this reason, in the supply apparatus 1d, the utilization efficiency of the organometallic compound is high. Therefore, according to the supply apparatus 1d, the carrier gas containing the organometallic compound at a concentration equal to or higher than a predetermined concentration can be supplied over a long period from the discharge port. That is, according to the supply apparatus 1d, the organometallic compound-containing gas can be stably supplied over a long period of time.
(Experimental example 3)
44 cc of alumina spheres with a diameter of 0.5 mm are arranged at the lowermost part of the inner space of the container 20, and a mixture of 24.9 g (48 cc) of Cp2Mg and 44 cc of alumina spheres with a diameter of 0.5 mm is placed thereon. Furthermore, 66 cc of alumina spheres having a diameter of 0.5 mm were arranged thereon. A mixture of 1.90 g (4 cc) of Cp2Mg and 8 cc of alumina spheres having a diameter of 0.5 mm was disposed at the lowermost part of the internal space of the container 20, and 8 cc of alumina spheres having a diameter of 0.5 mm were disposed thereon. . Otherwise, an organometallic compound-containing gas supply device was produced under the same conditions as in Experimental Example 1.
(Evaluation)
Argon gas was supplied as a carrier gas at 2000 ccm to the organometallic compound-containing gas supply device prepared in Experimental Example 3 under the conditions of 60 ° C. and 760 Torr. At that time, the amount of Cp2Mg extracted per unit time (removal speed) in the gas supplied from the supply device was measured. The ratio of the amount of Cp2Mg taken out until the takeout speed becomes 5% of the takeout speed at the beginning of use with respect to the charged amount of Cp2Mg (until the takeout speed becomes 5% of the takeout speed at the beginning of use) The amount of Cp2Mg taken out in (3) / the amount of Cp2Mg charged) was determined as the stable end point (%). As a result, as described above, in Experimental Example 2, the stable extraction end point was about 75%, whereas in Experimental Examples 1 and 3, the stable extraction end point was about 95%.

(Sixth embodiment)
FIG. 7 is a schematic cross-sectional view of an organometallic compound-containing gas supply device 1e according to the sixth embodiment.

As shown in FIG. 7, in the supply device 1 e, a diffusion layer 25 is disposed on the upstream side of the supply unit 23. The diffusion layer 25 has substantially the same configuration and the same function as the diffusion layer 15. By disposing the diffusion layer 25, the carrier gas can be uniformly supplied to the entire supply unit 23.

1, 1a, 1b, 1c, 1d, 1e

Supply device

10, 20

Container

10a, 20a Internal space 10a1 First region 10a2

Second region

10b,

20b Inlet port

10c,

20c Discharge port

13, 23 Supply unit 14 High specific gravity Material layer 14a First high specific gravity layer 14b Second high

specific gravity layer

15, 25 Diffusion layer 21 Filler layer

Claims

An apparatus for supplying a gas containing an organometallic compound that is solid at room temperature,
A container having an internal space, a carrier gas inlet connected to a lower portion of the internal space, and a discharge port connected to an upper portion of the internal space;
A supply section located in the internal space, in which a mixture of organometallic compound-containing particles and filler is disposed;
In the internal space, arranged on the supply unit, a high specific gravity material having a higher specific gravity than the organometallic compound-containing particles,
An apparatus for supplying an organometallic compound-containing gas.
The organometallic compound-containing gas supply device according to claim 1, wherein the high specific gravity material is disposed so as to cover the supply unit.
The supply of the organometallic compound-containing gas according to claim 1, wherein the high specific gravity includes a first high specific gravity and a second high specific gravity having a higher specific gravity than the first high specific gravity. apparatus.
4. The organometallic compound-containing gas supply device according to claim 3, wherein the second high specific gravity material is disposed on the first high specific gravity material.
The apparatus for supplying an organometallic compound-containing gas according to claim 3, wherein the first high-specific gravity material and the second high-specific gravity material are mixed and arranged.
The organometallic compound-containing gas supply device according to any one of claims 1 to 5, wherein the specific gravity of the high specific gravity material is 1.01 or more times that of the organometallic compound-containing particles.
An internal space; a carrier gas introduction port connected to the internal space; and a discharge port connected to the internal space and connected to the discharge port of the container. Another container including a first part on the mouth side and a second part located on the outlet side from the first part;
An organometallic compound disposed in the first portion;
A filler filled in the second portion;
With
When 60% or more of the organometallic compound in the container is consumed, the air resistance of the carrier gas in the second portion is higher than the air resistance of the carrier gas in the first portion. The organometallic compound-containing gas supply device according to any one of claims 1 to 6, wherein the portion 2 is filled with the filler.
The device for supplying an organometallic compound-containing gas according to claim 7, wherein an end of the first part on the second part side and the second part are tapered toward the discharge port side. .
The organometallic compound according to claim 7 or 8, wherein when 60% or more of the organometallic compound in the container is consumed, the porosity in the second portion is lower than the porosity in the first portion. Supply device for contained gas.
The first portion is filled with an organometallic compound supported on a carrier;
The organometallic compound-containing gas supply device according to any one of claims 7 to 9, wherein an average particle diameter of the filler is equal to or less than an average particle diameter of the carrier.
The first portion is filled with a mixture of a filler and the organometallic compound,
The organic metal according to any one of claims 7 to 9, wherein an average particle diameter of the filler disposed in the second portion is equal to or less than an average particle diameter of the filler disposed in the first portion. Compound gas supply device.
12. The organometallic compound-containing gas supply device according to claim 1, wherein the filler content in the mixture is 20% by volume to 80% by volume.
The organometallic compound is an organolithium compound, an organoindium compound, an organozinc compound, an organoaluminum compound, an organogallium compound, an organomagnesium compound, an organobismuth compound, an organomanganese compound, an organoiron compound, an organobarium compound, an organostrontium compound, The apparatus for supplying an organometallic compound-containing gas according to any one of claims 1 to 12, which is at least one selected from the group consisting of an organic copper compound, an organic calcium compound, an organic yttrium compound, and an organic cobalt compound.