KR20160137961A - Organic metal compound-containing gas supply device - Google Patents

Abstract

[PROBLEMS] To provide an apparatus for supplying an organometallic compound capable of stably supplying an organometallic compound-containing gas over a long period of time.
[MEANS FOR SOLVING PROBLEMS] An apparatus (1) for supplying an organometallic compound-containing gas includes a vessel (10), a supply unit (13), and a high boiling point water. The vessel 10 has an inner space 10a, an inlet 10b for the carrier gas, and an outlet 10c. The introduction port 10b is connected to the lower portion of the inner space 10a. The discharge port 10c is connected to the upper portion of the inner space 10a. The supply part 13 is located in the inner space 10a. A mixture of the organometallic compound-containing particles and the filler is disposed in the supply portion 13. The high boiling water is disposed on the supply portion 13 in the internal space 10a. The high boiling water has a higher boiling point than the particles containing the organometallic compound.

Description

TECHNICAL FIELD [0001] The present invention relates to an apparatus for supplying an organometallic compound-

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

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

Japanese Patent Application Laid-Open No. 2009-127096

There is a demand to supply an organometallic compound-containing gas within a predetermined concentration range from a supply device for the organic metal compound-containing gas. That is, it is demanded that the apparatus for supplying an organometallic compound-containing gas can stably supply an organometallic compound-containing gas over a long period of time.

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

The apparatus for supplying an organometallic compound-containing gas according to the present invention is an apparatus for supplying a gas containing an organometallic compound which is solid at room temperature. The apparatus for supplying an organometallic compound-containing gas according to the present invention comprises a container, a supply portion, and a high boiling point water. The vessel has an inner space, an inlet for the carrier gas, and an outlet. The introduction port is connected to the lower portion of the inner space. The discharge port is connected to the upper portion of the inner space. The supply part is located in the inner space. A mixture of the organometallic compound-containing particles and the filler is disposed in the supply part. The high boiling water is disposed on the supply portion in the internal space. The high boiling water has a higher boiling point than the particles containing the organometallic compound.

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

1 is a schematic cross-sectional view of a device for supplying an organometallic compound-containing gas according to the first embodiment.
Fig. 2 is a graph schematically showing the concentration of the organometallic compound in the organometallic compound-containing gas in the case where no heavier water is provided.
3 is a schematic cross-sectional view of the apparatus for supplying an organometallic compound-containing gas according to the second embodiment.
4 is a schematic cross-sectional view of the apparatus for supplying an organometallic compound-containing gas according to the third embodiment.
5 is a schematic cross-sectional view of a supply apparatus for an organometallic compound-containing gas according to the fourth embodiment.
6 is a schematic cross-sectional view of a supply apparatus for an organometallic compound-containing gas according to the fifth embodiment.
7 is a schematic cross-sectional view of a device for supplying an organometallic compound-containing gas according to the sixth embodiment.
8 is a schematic cross-sectional view of a device for supplying an organometallic compound-containing gas produced in Experimental Example 1. Fig.

Hereinafter, an example of a preferred embodiment of the present invention will be described. However, the following embodiments are merely examples. The present invention is not limited to the following embodiments at all.

In the drawings referred to in the embodiments 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 shown. The ratio of the dimension of the object drawn in the drawing may be different from the ratio of the dimension of the actual object or the like. Even in the drawings, the dimensional ratios and the like of the objects may be different. The specific dimensional ratio of the object, etc. should be judged based on the following description.

(First Embodiment)

1 is a schematic cross-sectional view of a device for supplying an organometallic compound-containing gas according to the first embodiment. The apparatus 1 for supplying an organometallic compound-containing gas shown in Fig. 1 is an apparatus for supplying a gas containing an organometallic compound which is solid at room temperature. Specifically, a carrier gas is supplied to the feeder 1. The supply device 1 is a device for supplying a mixed gas of a carrier gas and an organometallic compound which is solid at room temperature.

The kind of the organometallic compound which is solid at room temperature is not particularly limited. Specific examples of the organometallic compound which is solid at room temperature include organic lithium compounds, organic indium compounds, organic zinc compounds, organoaluminum compounds, organic gallium compounds, organomagnesium compounds, organic bismuth compounds, organic manganese compounds, An organic barium compound, an organic strontium compound, an organic copper compound, an organic calcium compound, an organic ytterbium compound, and an organic cobalt compound. Specific examples of the organolithium compound include t-butyllithium and the like. Specific examples of the organic indium compound include trimethyl indium, dimethyl chloro indium, cyclopentadienyl indium, trimethyl indium · trimethyl arsine duct, trimethyl indium · trimethyl phosphine duct, and the like. Specific examples of the organic zinc compound include, for example, zinc ethyl iodide, ethyl cyclopentadienyl zinc, and cyclopentadienyl zinc. Specific examples of the organoaluminum compound include methyldichloroaluminum, triphenylaluminum, tris (dimethylamido) aluminum, and the like. Specific examples of the organic gallium compound include, for example, methyldichlorogallium, dimethylchlorogallium, dimethylbromogallium and the like. Specific examples of the organomagnesium compound include, for example, bis (cyclopentadienyl) magnesium, bis (dimethylamido) magnesium, and the like. Specific examples of the organic bismuth compound include triphenylbismuth and the like. Specific examples of the organic manganese compound include, for example, bis (cyclopentadienyl) manganese, bis (dimethylamido) manganese, and the like. Specific examples of the organic iron compound include ferrocene and the like. Specific examples of the organic barium compound include bis (acetylacetonato) barium, dipivaloylmethanatobarbital, 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, dipivaloylmethanato copper, and the like. Specific examples of the organic calcium compound include bis (acetylacetonato) calcium, dipivaloylmethanato calcium, and the like. Specific examples of the organic ytterbium compound include dipivaloylmethanatoidebum and the like. Specific examples of the organic cobalt compound include bis (dimethylamido) cobalt, (t-butylmethylacetylene) (hexacarbonyl) dicobalt, and the like.

The feeder 1 includes a container 10, a feeder 13, and a high-boiling water.

The vessel 10 has an inner space 10a, an inlet 10b, and an outlet 10c. The inner space 10a may be, for example, a columnar shape. Specifically, the inner space 10a may be, for example, a cylindrical shape, a columnar shape, or the like. In the present embodiment, the inner space 10a is a columnar shape.

The introduction port 10b is connected to the lower portion of the inner space 10a. The discharge port 10c is connected to the upper portion of the inner space 10a. Therefore, the carrier gas supplied from the introduction port 10b flows in the inner space upward from below, and is discharged from the discharge port 10c. Specifically, in the present embodiment, the introduction port 10b is provided on the bottom wall of the container 10. The discharge port 10c is provided on the upper wall of the vessel 10.

The supply unit 13 supplies the organometallic compound gas to the carrier gas. By supplying the organometallic compound gas from the supply portion 13, an organometallic compound-containing gas is produced.

The supply part 13 is located in the inner space 10a. The internal space 10a has a first area 10a1 and a second area 10a2 located on the first area 10a1. The supply unit 13 is disposed in the first area 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.

A mixture of the organometallic compound-containing particles and the filler is disposed in the supply portion 13.

The organic metal compound-containing particles may be particles containing an organic metal compound, or may be particles having a carrier and an organometallic compound carried on the carrier. The carrier may be composed of, for example, inorganic oxide particles, metal particles, resin particles and the like. Examples of the carrier include alumina, silica, mullite, gracicarbon, graphite, potassium titanate, sponge titanium, quartz, silicon nitride, boron nitride, silicon carbide, stainless steel, aluminum, nickel, titanium, tungsten, And the like.

The specific gravity of the organic metal 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, more preferably 0.05 mm to 8.0 mm.

The organometallic compound-containing particles may be spherical, or may be amorphous such as pulverized product.

The filler is a particle that does not substantially contain an organometallic compound. The filler can be composed of, for example, inorganic oxide particles, metal particles, resin particles and the like. The filler may be selected from, for example, alumina, silica, mullite, glaucicarbon, graphite, potassium titanate, sponge titanium, quartz, silicon nitride, boron nitride, silicon carbide, stainless steel, aluminum, nickel, titanium, tungsten, 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 shaped material such as ground material.

The specific gravity of the filler is preferably 1.0 g / ml to 15.0 g / ml, 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, more preferably 0.1 mm to 8.0 mm.

In the inner space 10a, a high-boiling water is disposed on the supply unit 13. [ The high boiling water is located in a part of the second region 10a2. Specifically, the high-boiling water is disposed in a part of the lower side in the vertical direction of the second area 10a2. The high boiling water is disposed at a portion of the second region 10a2 excluding the upper portion. In the present embodiment, the upper portion in the vertical direction of the second region 10a2 is a space.

The shape of the high boiling water is not particularly limited. The high boiling water may be, for example, a plate-like material, but is particulate in this embodiment. A plurality of high-boiling water are provided on the supply unit 13. A plurality of high-boiling water are provided in layers on the supply unit (13). The plurality of high boiling water constitutes the high boiling water layer (14) located on the supply part (13). Substantially all of the supply portion 13 is covered with the high-boiling water layer 14. Above all, in the present invention, it is not necessarily required to arrange a plurality of high-boiling water. For example, a single plate-like high-boiling water having a plurality of through holes may be disposed on the supply unit 13. [

However, from the viewpoint of filling more of the organometallic compound in the container, it is also conceivable to charge only the particles of the organometallic compound in the container. However, the inventors of the present invention have found that, when only the organometallic compound is charged in the vessel, the carrier gas containing the organometallic compound becomes difficult to be supplied from the discharge port over a long period of time at a concentration of a predetermined concentration or more. The reason therefor is not clear, but the following reasons can be considered. That is, in the internal space, it is considered that sublimation and aggregation of the organometallic compound occur repeatedly. For example, it is considered that the sublimation amount of the organometallic compound becomes larger than the aggregation amount of the organometallic compound at the upstream portion where the carrier gas having a low concentration of the organometallic compound flows in the inner space. On the other hand, it is considered that the aggregation amount of the organometallic compound becomes larger than the sublimation amount of the organometallic compound in the downstream portion where the carrier gas having a high concentration of the organometallic compound flows in the inner space. As a result, in the downstream portion of the internal space, grain growth of the organic metal compound-containing particles may occur. Along with this, adjacent particles are bonded to each other, and a portion having a high air permeability resistance and a portion having a low air permeability resistance may be formed on the downstream side portion of the internal space. It is conceivable that a so-called channeling occurs in which the carrier gas preferentially passes through a portion having lower air permeability resistance than other portions. When channeling occurs, the organometallic compound located in the vicinity of the portion with low air flow resistance is preferentially consumed, and the organic metal compound located in the portion having high air flow resistance is hardly consumed. As a result, the consumption of the organic metal compound until the concentration of the organic metal compound in the mixed gas is lower than the predetermined concentration may be reduced.

In the apparatus 1 for supplying the organometallic compound-containing gas, a mixture of the organometallic compound-containing particles and the particulate filler is disposed in the internal space 10a. As a result, there is a portion where the filler intervenes between adjacent organic metal compound-containing particles. Therefore, even when the aggregation amount of the organometallic compound is larger than the sublimation amount of the organometallic compound, the portion where the organometallic compounds are adjacent to each other is small, thereby suppressing the occurrence of channeling accompanying the bonding of the organometallic compound-containing particles. Therefore, according to the supply apparatus 1, it is possible to increase the consumption amount of the organic metal compound until the concentration of the organic metal compound in the mixed gas is lower than the predetermined concentration.

It is preferable that the content of the filler in the supply part 13 is 20% by volume to 80% by volume from the viewpoint of increasing the consumption amount of the organic metal compound until the concentration of the organic metal compound in the mixed gas is lower than the predetermined concentration, , More preferably from 30% by volume to 70% by volume.

The arrangement of the mixture of the organometallic compound particles and the filler particles is more effective when the melting point is high and it is difficult to support the organometallic compound on the carrier. Therefore, it is preferable to use, as the organometallic compound, an organic lithium compound, an organic indium compound, an organic zinc compound, an organoaluminum compound, an organic gallium compound, an organomagnesium compound, an organic bismuth compound, an organic manganese compound, , The organic copper compound, the organic calcium compound, the organic ytterbium compound and the organic cobalt compound is used, the supply device 1 is more useful.

As a result of intensive studies, the inventors of the present invention have found that when a mixture of an organometallic compound-containing particle and a particulate filler is disposed in the inner space 10a, the organometallic compound And the concentration of the water-soluble polymer is excessively high. Specifically, as shown in the schematic graph shown in Fig. 2, the concentration of the organometallic compound in the organic metal compound-containing gas immediately after the start of the supply of the carrier gas becomes steadily high once stabilized. The concentration of the organic metal compound in the organic metal compound-containing gas becomes lower than the permissible lower limit value C1 and the allowable upper limit value C1 until the concentration of the organic metal compound is stabilized after the supply of the carrier gas is started, C2. ≪ / RTI > Further, 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 becomes lower than 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 becomes shorter.

As a result of further intensive studies, the inventors of the present invention have found that the above phenomenon occurs because at least the upper portion of the mixture disposed in the supply portion 13 is floated together with the carrier gas at the start of supply of the carrier gas. When at least the upper part of the mixture disposed in the supply part 13 floats together with the carrier gas, the organometallic compound-containing particles and the filler are aggregated downward in the specific gravity, and the light gravity aggregates in the upper part. Normally, the specific gravity of the organometallic compound-containing particles is lower than the specific gravity of the filler, so that the organometallic compound-containing particles are gathered at the top. As a result, a layer having a high concentration of the organic metal compound-containing particles is formed. As a result, it is considered that the concentration of the organic metal compound in the organic metal compound-containing gas temporarily increases.

Therefore, in this embodiment, high-boiling water having a higher boiling point than that of the organometallic compound-containing particles is disposed on the supply unit 13. It is possible to suppress the floating of the organometallic compound-containing particles or the filler disposed in the supply portion 13 at the start of the supply of the carrier gas. Therefore, as shown in FIG. 2, it is possible to suppress the concentration of the organic metal compound from exceeding the allowable upper limit value C2 at the start of supply of the carrier gas. In addition, since excessive consumption of the organic metal compound is unlikely to occur at the start of the supply of the carrier gas, it is possible to supply the organometallic compound-containing gas with the concentration lower than the lower limit of the allowable limit C1 over a long period of time. Therefore, the supplyable period T2 of the organometallic compound-containing gas at the concentration located between the allowable lower limit value C1 and the allowable upper limit value C2 can be lengthened.

It is preferable to dispose the high boiling point material so as to cover the supply portion 13 from the viewpoint of making the period for supplying the organometallic compound-containing gas of a predetermined concentration longer. From this point of view, it is preferable that a high-boiling water layer 14 containing a plurality of high boiling water is provided on the supply part 13. [

The specific gravity of the high boiling point water 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 functions substantially common to those of the first embodiment are referred to by common reference numerals, and a description thereof will be omitted.

(Second Embodiment)

3 is a schematic cross-sectional view of the apparatus 1a for supplying an organometallic compound gas according to the second embodiment. As shown in Fig. 3, in this embodiment, the high boiled water layer 14 has the first high boiled water layer 14a and the second high boiled water layer 14b. The second high-boiler layer 14b is located on the first high-boiler layer 14a. The specific gravity of the second high-boiling water disposed in the second high boiler layer 14b is higher than the specific gravity of the first high boiler disposed in the first high boiler layer 14a. By further providing the second high-boiling water layer 14b including the high-boiling high-boiling water as described above, it is possible to more effectively suppress the scattering of the organic-metal-compound-containing particles and the filler at the start of the supply of the carrier gas .

In the present embodiment, an example in which the second high-boiling water is disposed on the first high boiling water has been described. However, the present invention is not limited to this configuration. The first high boiling water and the second high boiling water may be mixed and disposed.

(Third Embodiment)

4 is a schematic cross-sectional view of the apparatus 1b for feeding an organometallic compound-containing gas according to the third embodiment. 4, in the supply device 1b, the diffusion layer 15 is disposed under the supply portion 13 (on the introduction port 10b side) in the internal space 10a. By providing the diffusion layer 15, it is possible to uniformly supply the carrier gas to the entire supply portion 13. Further, the diffusion layer 15 can be made of, for example, a filler.

(Fourth Embodiment)

5 is a schematic cross-sectional view of the apparatus 1c for feeding an organometallic compound-containing gas according to the fourth embodiment.

In the first to third embodiments, an example in which the apparatus for supplying the organometallic compound-containing gas has only one vessel 10 has been described. However, the present invention is not limited to this configuration. For example, as shown in Fig. 5, the feeding device 1c has a container 20, in addition to the container 10. Fig. The container 20 is connected in series with respect to the container 10. Concretely, a discharge port 20c connected to the internal space 20a of the container 20 is connected to the inlet port 10b of the container 10. The carrier gas inlet 20b of the container 20 is provided at the upper portion of the container 20 and the outlet 20c is provided at the lower portion of the container 20. For this reason, in the vessel 20, the carrier gas flows downward from above.

The supply unit 23 is substantially the same as the supply unit 13. [ The supply part (23) is provided with particles of an organometallic compound and a filler.

A filler layer 21 in which a filler is disposed is provided below the supply part 23.

However, it is required that the organometallic compound-containing gas supply device is capable of stably supplying the organometallic compound-containing gas over a long period of time. That is, it is preferable that a carrier gas containing an organometallic compound at a concentration of a predetermined concentration or more is supplied from the discharge port over a long period of time. In order to realize this, it is important to increase the consumption amount of the organic metal compound until the concentration of the organic metal compound in the mixed gas is lower than the predetermined concentration.

The reason why the consumption amount of the organic metal compound until the concentration of the organic metal compound in the mixed gas is lower than the predetermined concentration is considered to be as follows. And a so-called channeling in which the carrier gas preferentially passes through the portion where the air-flow resistance of the carrier gas is low is considered to occur. When channeling occurs, the organometallic compound located in the vicinity of the portion with low air flow resistance is preferentially consumed, and the organic metal compound located in the portion having high air flow resistance is hardly consumed. As a result, the consumption of the organic metal compound until the concentration of the organic metal compound in the mixed gas is lower than the predetermined concentration may be reduced.

The amount of the carrier gas in the entirety of the filler layer 21 is larger than the permeation resistance of the carrier gas in the entire supply part 23 when the organometallic compound in the container 20 is consumed more than 60% The filling material layer 21 is filled with a filler. Therefore, when more than 60% of the organometallic compound in the vessel 20 is consumed, the filler layer 21 having a relatively high aeration resistance of the carrier gas exists, A portion lower than the portion is less likely to occur. Therefore, the carrier gas passes through the supply portion 23 with high uniformity. As a result, the consumption of the organic metal compound until the concentration of the organic metal compound in the mixed gas is lower than the predetermined concentration can be increased. That is, according to the supply apparatus 1, a carrier gas containing an organic metal compound can be supplied from the discharge port over a long period of time at a concentration of a predetermined concentration or more.

The ventilation resistance of the carrier gas in the entire filler layer 21 is made higher than the ventilation resistance of the carrier gas in the entire supply portion 23 when more than 60% of the organometallic compound in the vessel 20 is consumed As a concrete method, for example, a method may be considered in which the porosity in the filler layer 21 is lower than the porosity in the supply portion 23 when more than 60% of the organometallic compound in the vessel 20 is consumed . As an example of a method for realizing this, it is conceivable to set the average particle diameter of the filler filled in the filler layer 21 to be equal to or smaller than the average particle diameter of the carrier of the carrier charged in the supply part 23. [ When the supply portion 23 is filled with the mixture of the filler and the organometallic compound, the average particle diameter of the filler filled in the filler layer 21 may be made equal to or smaller than the filler average particle diameter of the supply portion 13 .

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 compound) / (the amount of the organic metal compound in the container 20 before use of the supply device 1c) is less than or equal to 40%, the flow resistance of the carrier gas in the entire supply part 23, The filler layer 21 may be filled with a filler so that the flow resistance of the carrier gas throughout the filler layer 21 becomes high. For example, when ((the amount of the organometallic compound remaining in the container 20) / (the amount of the organometallic compound in the container 20 before use of the supply device 1c) is not more than 40% The filler layer 21 may be filled with a filler so that the permeation resistance of the carrier gas in the filler layer 21 is higher than the permeation resistance of the carrier gas in the entire supply portion 23 .

In the present embodiment, the portion of the inner space 20a on the side of the discharge port 20c is tapered toward the discharge port 20c side. Concretely, the end of the supply part 23 on the side of the filler layer 21 and the filler layer 21 are tapered toward the discharge port 20c as a whole. As a result, it is possible to suppress the supply of the carrier gas to a part of the supply part 23, and uniform carrier gas can be supplied to the entire supply part 23. As a result, the consumption of the organic metal compound until the concentration of the organic metal compound in the mixed gas is less than the predetermined concentration can be increased.

(Experimental Example 1)

In Experimental Example 1, the apparatus for feeding the organometallic compound-containing gas shown in Fig. 8 was produced under the following conditions.

Container 20:

The tapered portion at the lower end of the inner space: 10.1 cc

Circumferential portion excluding the taper portion of the lower end of the inner space: 182.4 cc

21 cc of alumina spheres having a diameter of 0.5 mm was placed in the lowermost part of the inner space, and a mixture of 24.9 g (48 cc) of Cp2Mg and 42 cc of alumina spheres having a diameter of 0.5 mm was placed thereon. I placed an old 86cc.

Container (10):

At the lower end of the inner space, a 1.1 cc tapered portion that is thicker toward the upper side was provided.

The circumferential portion excluding the taper portion of the internal 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 placed at the lowest part of the inner space, and 8 cc of alumina spheres having a diameter of 0.5 mm was disposed thereon.

(Experimental Example 2)

A mixture of 24.61 g (50 cc) of Cp2Mg and 44 cc of alumina spheres having a diameter of 0.5 mm was disposed at the lowermost part of the inner space of the container 20, and 109 cc of alumina spheres 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 was disposed at the lowermost part of the inner space of the vessel 10, and 9cc of alumina spheres having a diameter of 0.5 mm was arranged thereon. Except for the above, an apparatus for supplying an organometallic compound-containing gas was produced under the same conditions as in Experimental Example 1. [

(evaluation)

Argon gas was flowed as a carrier gas at 2000 cc at 60 DEG C under a pressure of 760 Torr in a feeding apparatus for the organometallic compound-containing gas produced in Experimental Example 1 and Experimental Example 2, respectively. At that time, the amount of Cp2Mg taken out per unit time (take-out speed) in the gas supplied from the supply device was measured. The ratio of the amount of Cp2Mg taken out until the take-out speed became 5% of the take-out speed at the beginning of use, the ratio to the amount of Cp2Mg (the take-out speed was Cp2Mg taken out until 5% / Cp2Mg) was obtained as the stable extraction end point (%). As a result, in Experimental Example 2, the stable extraction end point was about 75%, while in Experimental Example 1, the stable extraction end point was about 95%.

(Fifth Embodiment)

6 is a schematic cross-sectional view of the apparatus 1d for feeding an organometallic compound-containing gas according to the fifth embodiment.

From the viewpoint of filling more 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 of the present invention have found that it is not possible to stably supply an organometallic compound-containing gas over a long period of time by filling the tapered second portion with an organometallic compound. That is, the present inventors have found that when a tapered second portion is filled with an organometallic compound, a carrier gas containing an organometallic compound at a concentration of a predetermined concentration or more can not be supplied from the discharge port over a long period of time.

The reason for this is not clear, but the flow rate of the carrier gas at the portion near the side wall of the second portion of the tapered shape is smaller than the flow rate of the carrier gas at the other portion, And the use efficiency of the organometallic compound disposed in the portion is lowered.

Therefore, as shown in Fig. 6, in the supply device 1d, the filler layer 21 is located above the tapered portion in addition to the tapered portion of the internal space 20a. As a result, the utilization efficiency of the organometallic compound is high in the supply device 1d. Thus, according to the supply device 1d, the carrier gas containing the organic metal compound can be supplied from the discharge port over a long period of time at a concentration of a predetermined concentration or more. That is, according to the supply device 1d, it is possible to stably supply the organometallic compound-containing gas over a long period of time.

(Experimental Example 3)

44 cc of alumina spheres having a diameter of 0.5 mm was 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 having a diameter of 0.5 mm was placed thereon, And 66 cc of alumina spheres having a diameter of 0.5 mm were arranged. A mixture of 1.90 g (4 cc) of Cp2Mg and 8 cc of alumina spheres having a diameter of 0.5 mm was placed at the lowermost portion of the inner space of the container 20, and 8 cc of alumina spheres having a diameter of 0.5 mm was disposed thereon. Except for the above, an apparatus for supplying an organometallic compound-containing gas was produced under the same conditions as in Experimental Example 1. [

(evaluation)

Argon gas was flowed as a carrier gas at 2000 cc at 60 DEG C under 760 Torr to the apparatus for feeding the organometallic compound-containing gas produced in Experimental Example 3. [ At that time, the amount of Cp2Mg taken out per unit time (take-out speed) in the gas supplied from the supply device was measured. The ratio of the amount of Cp2Mg taken out until the take-out speed became 5% of the take-out speed at the beginning of use, the ratio to the amount of Cp2Mg (the take-out speed was Cp2Mg taken out until 5% / Cp2Mg) was obtained as the stable extraction end point (%). As a result, as described above, in Experimental Example 2, the stable extraction end point was about 75%, while 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 the apparatus 1e for feeding an organometallic compound-containing gas according to the sixth embodiment.

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

1, 1a, 1b, 1c, 1d, 1e:
10, 20: container
10a, 20a: inner space
10a1: first region
10a2: second region
10b, 20b: introduction port
10c, 20c: outlet
13, 23:
14: heavy water layer
14a: first high-boiling water layer
14b: second high-boiling water layer
15, 25: diffusion layer
21: filler layer

Claims (13)

An apparatus for supplying a gas containing an organometallic compound which is solid at room temperature,
A container having an inner space, an introduction port for a carrier gas connected to a lower portion of the inner space, and an outlet connected to an upper portion of the inner space,
A supply part located in the internal space, in which a mixture of the organometallic compound-containing particles and the filler is disposed,
Wherein the organic metal compound-containing particles are disposed on the supply portion in the internal space,
And a gas supply unit for supplying the organometallic compound-containing gas. The apparatus for supplying an organometallic compound-containing gas according to claim 1, wherein the heavier water is disposed to cover the supply portion. The apparatus for supplying an organometallic compound-containing gas according to claim 1 or 2, wherein the high boiling point water comprises a first high boiling point water and a second high boiling point water having a higher boiling point than the first high boiling point water. The apparatus for supplying an organometallic compound-containing gas according to claim 3, wherein the second high boiling point water is disposed on the first high boiler water. The apparatus for supplying an organometallic compound-containing gas according to claim 3, wherein the first high boiling point water and the second high boiling point water are mixed and arranged. The apparatus for supplying an organometallic compound-containing gas according to any one of claims 1 to 5, wherein the specific gravity of the high boiling point water is 1.01 or more times the specific gravity of the organometallic compound-containing particles. 7. The fuel cell system according to any one of claims 1 to 6, further comprising: an internal space; an introduction port for the carrier gas connected to the internal space; and an outlet connected to the outlet of the container, A separate container including the first portion of the inlet and the second portion located on the outlet side of the first portion,
An organometallic compound disposed in the first portion,
The filler filled in the second portion
And,
Wherein the second portion is provided with a first portion and a second portion, the second portion being configured such that, when at least 60% of the organometallic compound in the container is consumed, the air flow resistance of the carrier gas in the second portion is higher than the air resistance of the carrier gas in the first portion Wherein the filler is filled with the organometallic compound-containing gas. The apparatus for supplying an organometallic compound-containing gas according to claim 7, wherein an end portion of the first portion on the second portion side and the second portion are tapered toward the discharge port side. The method according to claim 7 or 8, wherein, when at least 60% of the organometallic compound in the vessel is consumed, the porosity of the second portion is lower than the porosity of the first portion, / RTI > 10. The method according to any one of claims 7 to 9, wherein the first portion is filled with the organometallic compound supported on the support,
Wherein an average particle diameter of the filler is not more than an average particle diameter of the support. 10. The method according to any one of claims 7 to 9, wherein the first portion is filled with a mixture of a filler and the organometallic compound,
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. The apparatus for supplying an organometallic compound-containing gas according to any one of claims 1 to 11, wherein the content of the filler in the mixture is 20% by volume to 80% by volume. The organic electroluminescent device according to any one of claims 1 to 12, wherein the organometallic compound is at least one selected from the group consisting of an organolithium compound, an organic indium compound, an organic zinc compound, an organic aluminum compound, an organic gallium compound, an organomagnesium compound, an organic bismuth compound, Wherein the organic metal compound-containing gas is at least one selected from the group consisting of organic iron compounds, organic barium compounds, organic strontium compounds, organic copper compounds, organic calcium compounds, organic ytterbium compounds and organic cobalt compounds.

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