JP5262083B2 - Solid organometallic compound feeder - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To stably feed an organic metal compound over many hours in a feeding device for feeding a solid organic metal compound together with a carrier gas at room temperature. <P>SOLUTION: The feeder is provided with two column-like vessels 1a and 1b, a communicating tube 5 for communicating the interior of the vessels 1a and 1b at the lower end thereof. A gas-guiding tube 2 and 3 are provided at the upper part of the vessel 1a and 1b, respectively. The interior of the vessel 1a is filled with an organic metal compound 10 and a dispersing member 11 for dispersing the carrier gas introduced from the gas conductive tube 2, in this order, from the bottom of the vessel 1a. The other vessel 1b is filled with the organic metal compound 10. <P>COPYRIGHT: (C)2009,JPO&amp;INPIT

Description

  The present invention relates to a supply apparatus for supplying an organometallic compound together with a carrier gas by circulating the carrier gas in a container filled with a solid organometallic compound at room temperature.

  In the production of compound semiconductor devices, the MOCVD method (metal organic chemical vapor deposition method) is generally used. At this time, it is important to gasify and stably supply a solid organometallic compound at room temperature.

  Conventionally, as a supply device that gasifies and supplies a solid organometallic compound at room temperature, the one disclosed in Patent Document 1 is known. As shown in FIG. 9, a supply device disclosed in Patent Document 1 includes a container 101 filled with an organometallic compound, a tube 103 for introducing a carrier gas inserted from the upper part of the container 101, and a tube 103 and a disperser 105 installed at the bottom of 103. In the upper part of the container, a filling port 104 for filling the organic metal compound into the container 101 and a lead-out port 102 for leading the organometallic compound gas and the carrier gas to the outside of the container 101 are provided. Furthermore, the lower part of the container 101 is a narrow-diameter part whose inner diameter is narrower than that of the upper part.

However, in the structure as described above, there still remain problems such as formation of a flow path through which the carrier gas passes without sufficient contact between the organometallic compound and the carrier gas in the container 101. Therefore, the ratio of the organometallic compound that remains in the container 101 without being transported by the carrier gas is large, and as for the stable supply of the organometallic compound over a long period of time, a satisfactory apparatus has not yet been developed. It was.
Japanese Patent Publication No. 5-10320

  An object of the present invention is to provide an industrially suitable organometallic compound supply apparatus that can stably supply an organometallic compound that is solid at room temperature over a long period of time.

In order to achieve the above object, the supply device of the present invention is a supply device for supplying a solid organometallic compound accompanying a carrier gas at room temperature,
A column-type first container provided with a carrier gas inlet at the top;
A column-type second container provided with an outlet for the carrier gas at the top;
A communication member that is disposed below the first container and the second container and communicates the inside of the first container and the inside of the second container at its lower end;
Have
The first container is filled with a dispersion material for dispersing the organometallic compound and the carrier gas introduced from the introduction port in this order from the bottom of the first container, and the second container Is filled with the organometallic compound.
The supply device of the present invention is particularly one in which the second container is not filled with a filler.

  In the supply device of the present invention, it is preferable that the dispersion material is filled in a layered manner so as to cover the organometallic compound in the first container. Further, the dispersion material is an aggregate of a large number of members and can have a gap between the members. Although the shape of the member which comprises a dispersing material is arbitrary, it is preferable that it is spherical.

  Furthermore, in the present invention, the introduction port may include a gas introduction pipe attached to the first container so that the carrier gas introduced into the first container collides with the upper wall surface of the first container. . Alternatively, the introduction port may include a disperser that disperses the carrier gas introduced into the first container.

  INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide an industrially suitable organometallic compound supply apparatus that can stably supply an organometallic compound that is solid at room temperature for a long time.

(First embodiment)
Referring to FIG. 1, an organometallic compound supply apparatus according to a first embodiment of the present invention is shown. The supply device includes two column-type containers 1a and 1b arranged in parallel with a space between each other, and a communication pipe 5 that communicates the inside of the two containers 1a and 1b at the lower ends of the containers 1a and 1b. ing.

  A gas introduction pipe 2 that constitutes a gas introduction port for introducing a carrier gas into the container 1a is attached to the upper end of one container 1a. A gas outlet pipe 3 that constitutes a gas outlet for leading the gas in the container 1b to the outside is attached to the upper end of the other container 1b.

  Each container 1a, 1b is filled with an organometallic compound 10 that is solid at room temperature. Further, a dispersion material 11 for dispersing the carrier gas introduced from the gas introduction pipe 2 in the container 1 a is disposed on the organometallic compound 10 in the container 1 a on the side where the gas introduction pipe 2 is attached. Filled. That is, the container 1a is filled with the organometallic compound 10 and the dispersion material 11 in this order from the bottom of the container 1a. The dispersion material 11 is an aggregate of many members, and is filled in the container 1a with a gap between the members.

  Outside the containers 1a and 1b, a filling port 4 is provided at an intermediate portion between the gas introduction pipe 2 and the gas outlet pipe 3. The filling port 4 is configured to be openable and closable. By opening the filling port 4, the inside of one container 1 a can be filled with the organometallic compound 10 and the dispersion material 11, and the inside of the other container 1 b is filled with the organometallic compound 10. Can be filled.

  For filling the container 1a with the organometallic compound 10 and the dispersion material 11, a publicly known method can be used. For example, the organometallic compound 10 and the dispersion material 11 are filled into the container 1a by introducing the organometallic compound 10 and the dispersion material 11 into the container 1a in this order from the filling port in an inert gas atmosphere. be able to. Filling the container 1b with the organometallic compound 10 can be performed in the same manner.

  The carrier gas introduced into the container 1a from the gas introduction pipe 2 is not particularly limited as long as it is inert with respect to the organometallic compound 10 and the dispersion material 11 filled in the containers 1a and 1b. Argon gas, nitrogen gas, helium gas, and hydrogen gas can be used. In addition, these carrier gas may be used independently and may be used in mixture of 2 or more types.

  As described above, the supply apparatus of the present embodiment fills the gas introduction pipe 2 with the carrier gas in a state where the container 1a is filled with the organometallic compound 10 and the dispersion material 11 and the container 1b is filled with the organometallic compound 10. In addition to being connected to the source, the gas outlet pipe 3 is connected to, for example, a vapor phase growth apparatus.

  Carrier gas is introduced into the supply device from the carrier gas source while the supply device is maintained at a constant temperature. The introduced carrier gas is supplied to the vapor phase growth apparatus through a path of the gas introduction pipe 2 → the container 1a → the communication pipe 5 → the container 1b → the gas outlet pipe 3. The organometallic compound 10 vaporized in each of the containers 1a and 1b accompanies the flow of the carrier gas, whereby the vaporized organometallic compound 10 is supplied to the vapor phase growth apparatus together with the carrier gas.

  In the course of the carrier gas flow in the supply device, the carrier gas introduced into the container 1 a first comes into contact with the dispersion material 11. Since the dispersion material 11 is an aggregate of many members as described above and has gaps between the members, the carrier gas in contact with the dispersion material 11 is formed by the gaps between the members. It flows toward the bottom of the container 1a through a large number of channels, and contacts the organometallic compound 10 in a wide range. As the carrier gas passes through the dispersion material 11 in this way, the carrier gas flow is dispersed by the dispersion material 11, so that the carrier gas can be brought into uniform contact with the organometallic compound 10. Accordingly, the carrier gas efficiently contacts the organometallic compound 10 and the vaporized organometallic compound 10 can be transported satisfactorily by the carrier gas. As a result, the organometallic compound 10 is stably supplied over a long period of time. be able to.

  In order to exhibit the dispersion of the carrier gas by the dispersion material 11 more effectively, the dispersion material 11 is filled in the container 1a so as to cover the organometallic compound 10 from above and form a layer. preferable.

  Further, the carrier gas that has been accompanied by the organometallic compound 10 and has reached the lower end of the container 1a is introduced into the container 1b from the lower end of the container 1b through the communication pipe 5, and further filled in the container 1b. After coming into contact with the organometallic compound 10, the inside of the container 1 b is raised and led out from the gas outlet pipe 3. By configuring the supply device so that the carrier gas flows through such a path, the carrier gas can be brought into contact with the organometallic compound 10 more efficiently, and the organometallic compound 10 can be supplied more stably. Can do.

  As long as the shape of the containers 1a and 1b is a column type, for example, a cylindrical shape, a triangular cylindrical shape, a square cylindrical shape, a hexagonal cylindrical shape, and the like can be used, and among these, the cylindrical container 1a 1b is preferably used. The shapes of the two containers 1a and 1b may be the same or different from each other.

  The total capacity of the two containers 1a and 1b is not particularly limited, but considering practicality, it is preferably in the range of 10 to 5000 ml, more preferably in the range of 10 to 3000 ml, particularly preferably 25 to 1000 ml. It is. The capacities of the containers 1a and 1b are different from each other in the example shown in FIG. 1, but may be the same as shown in FIG. When the capacities of the containers 1a and 1b are different from each other, in order to supply the organometallic compound 10 more stably over a long period of time, as shown in FIG. 1, the container 1a on the side into which the carrier gas is introduced, that is, the gas It is desirable that the capacity of the container 1a provided with the introduction pipe 2 is larger than the capacity of the container 1b provided with the gas outlet pipe 3. Furthermore, the ratio of the capacity of the container 1a provided with the gas introduction pipe 2 to the capacity of the container 1b provided with the gas outlet pipe 3 is preferably 1 to 80, more preferably 1 to 40. is there.

  The carrier gas circulates inside the containers 1a and 1b mainly in the axial direction of the containers 1a and 1b. Therefore, the inner dimensions of the containers 1a and 1b are set such that the ratio of the height to the diameter is 0.00 so that the carrier gas flowing in the containers 1a and 1b can efficiently come into contact with the organometallic compound 10 in the containers 1a and 1b. It is preferable that it is 8-10.0, More preferably, it is 1.2-10.0. This value assumes the case where the containers 1a and 1b are cylindrical, but when the container is not cylindrical, it may be considered as a circular diameter having an area equal to the cross-sectional area from the cross-sectional area.

  By setting the aspect ratio of the containers 1a and 1b within the above range, it is possible to suppress the formation of a gas flow path through which the carrier gas passes without contacting the organometallic compound 10 efficiently, and a stable organometallic compound. A supply amount of 10 can be maintained.

  The shape and structure of the communication pipe 5 are not particularly limited as long as they communicate with each other so that gas can flow between the two containers 1a and 1b. For example, by bending a single straight pipe, the two containers 1a, 1b are formed into a predetermined shape that can be connected at the lower end, a plurality of straight pipes connected to form a predetermined shape, and A U-shaped pipe or the like can be used as the communication pipe 5. From the viewpoint of designing the communication pipe 5, it is desirable that the communication pipe 5 is a straight pipe.

  The length of the communication pipe 5 is not particularly limited, and can be appropriately designed according to the size and arrangement of the two containers 1a and 1b. Further, the diameter of the communication pipe 5 is not particularly limited as long as the cross-sectional area of the communication pipe 5 is smaller than the cross-sectional area of the containers 1a and 1b at the connection portions with the containers 1a and 1b.

  As long as the gas introduction pipe 2 and the gas outlet pipe 3 are positioned at the upper ends of the containers 1a and 1b, the shape, size, and the attachment angle with respect to the containers 1a and 1b are not particularly limited.

  The dispersion material 11 used in the present invention is preferably formed of a material that is inert with respect to the organometallic compound 10 filled together in the container 1a. Examples of such materials include alumina, silica, mullite, glassy carbon, graphite, potassium titanate, sponge titanium, quartz, silicon nitride, boron nitride, silicon carbide, stainless steel, aluminum, nickel, titanium, tungsten, and fluorine resin. , Glass, zirconia, iron and the like. In addition, you may use these materials individually or in mixture of 2 or more types. Further, the shape of each member constituting the dispersion material 11 is not particularly limited, and for example, an indefinite shape, a spherical shape, a polyhedral shape, a fiber shape, a net shape, a spring shape, a coil shape, a cylindrical shape, or the like may be used. it can. Among these, it is preferable to use a spherical member because the carrier gas flow path formed in the gaps between the respective members can be uniformly dispersed when the dispersion material 11 is filled in the container 1a. For example, in the case of a spherical shape, the size of the dispersion material 11 is not particularly limited as long as it is a size that enters the container 1a from the filling port 4, but preferably has a diameter of 0.1 to 8.0 mm, and more preferably has a diameter of 0.1 to 6. 0 mm. Moreover, the size of the dispersion material 11 may be a uniform size or two or more sizes.

  Moreover, the filling amount of the dispersing material 11 depends on the size of the container 1a so that the carrier gas introduced into the container 1a from the gas introduction pipe 2 can be dispersed before coming into contact with the organometallic compound 10. It can be determined as appropriate. That is, it is filled so that the height of the layer of the dispersion material 11 filled in the container 1a is preferably 5 to 200 mm, more preferably 5 to 150 mm.

  Examples of the organic metal compound that is solid at room temperature used in the present invention include lithium compounds such as tert-butyllithium; trimethylindium, dimethylchloroindium, cyclopentadienylindium, trimethylindium / trimethylarsine adduct, trimethylindium / trimethyl Organic indium compounds such as phosphine adducts; Organic zinc compounds such as ethyl zinc iodide, ethylcyclopentadienyl zinc and cyclopentadienyl zinc; Organoaluminum compounds such as methyldichloroaluminum and triphenylaluminum; Methyldichlorogallium and dimethylchlorogallium Organic gallium compounds such as dimethylbromogallium; Magnesium compounds such as bis (cyclopentadienyl) magnesium; Bis such as triphenylbismuth Mass compounds; Manganese compounds such as bis (cyclopentadienyl) manganese; Iron compounds such as ferrocene; Barium compounds such as bis (acetylacetonato) barium, dipivaloylmethanatobarium and 1,10-phenanthroline adduct; Strontium compounds such as acetylacetonato) strontium and dipivaloylmethanatostrontium; copper compounds such as bis (acetylacetonato) copper and dipivaloylmethanatocopper; bis (acetylacetonato) calcium and dipivaloylmethanatocalcium And yttrium compounds such as dipivaloylmethanatoytium. In addition, the supply apparatus of this invention may be applicable also to the organic compound which does not contain a metal other than an organometallic compound, and the inorganic compound which contains or does not contain a metal.

  The organometallic compound may be supported on a carrier inert to the organometallic compound. Examples of the carrier material used in this case include alumina, silica, mullite, glassy carbon, graphite, potassium titanate, sponge titanium, quartz, silicon nitride, boron nitride, silicon carbide, stainless steel, aluminum, nickel, and titanium. , Tungsten, fluororesin, glass and the like are used. In addition, you may use these support | carriers individually or in mixture of 2 or more types. The shape of the carrier is not particularly limited, and for example, an indefinite shape, a round shape, a square shape, a spherical shape, a fiber shape, a net shape, a spring shape, a coil shape, a cylindrical shape, and the like can be used.

  In order to efficiently contact the organometallic compound supported on the carrier with the carrier gas, it is desirable that the specific surface area of the carrier is as large as possible. For that purpose, it is desirable to use a carrier having fine irregularities of about 100 to 2000 μm on the surface or a carrier having many pores (voids). Specific examples of such a carrier include, for example, alumina hole packing, Raschig rings (made of glass, made of Teflon (registered trademark)), helipack (made of glass, stainless steel), Dixon packing (made of stainless steel), Fenceke (made of glass). , Sponge titanium, stainless sintered element, glass wool and the like.

  In the embodiment described above, an example in which the filling port 4 is provided in the middle part of the gas introduction pipe 2 and the gas outlet pipe 3 has been shown. However, as shown in FIG. It can also be provided separately from the tube 2. Although not shown, the filling port 4 of the container 1b is provided separately from the gas outlet tube 3, or the charging port 4 of both the containers 1a and 1b is provided separately from the gas inlet tube 2 and the gas outlet tube 3. You can also.

(Second Embodiment)
FIG. 4 shows an organometallic compound supply apparatus according to a second embodiment of the present invention.

  In this embodiment, the shape of the gas introduction pipe 2 connected to the container 1a is different from that of the first embodiment. More specifically, the gas introduction pipe 2 is bent inside the container 1a so that the carrier gas introduced into the container 1a collides with at least the upper wall surface among the upper wall surface and the side wall surface inside the container 1a. The spout, which is the tip, faces upward. Other configurations may be the same as those in the first embodiment, and thus detailed description thereof is omitted.

  In the present embodiment, the carrier gas immediately after being introduced into the container 1a from the gas introduction pipe 2 collides with the upper wall surface inside the container 1a. When the carrier gas collides with the upper wall surface, the introduced carrier gas is dispersed inside the container 1a and contacts the dispersion material 11 in this state. Thereby, since carrier gas distribute | circulates in the wider range of the dispersion material 11, the dispersion | distribution effect | action of the carrier gas by the dispersion material 11 can be exhibited more effectively.

  In the example shown in FIG. 4, the distal end portion of the gas introduction pipe 2 is bent so as to introduce the carrier gas substantially perpendicularly to the upper wall surface of the container 1a, but the introduction angle of the carrier gas into the container 1a. There is no particular limitation as long as the carrier gas introduced into the container 1a collides with at least the upper wall surface of the upper wall surface and the side wall surface inside the container 1a.

  In the example shown in FIG. 4, the filling port 4 of the container 1 a is configured separately from the gas introduction pipe 2, and the capacities of the two containers 1 a and 1 b are different. However, the filling port 4 of the container 1a may be provided in the intermediate part of the gas introduction pipe 2, and the capacity | capacitance of the two containers 1a and 1b may be the same. Furthermore, the filling port 4 of the container 1 b may be configured separately from the gas outlet pipe 3.

  As a method of preliminarily dispersing the carrier gas introduced into the container 1a before coming into contact with the dispersion material 11, a method using a disperser provided inside the container 1a can be cited in addition to the example shown in FIG. .

  If a disperser is arrange | positioned inside the container 1a and the gas introduce | transduced in the container 1a can be disperse | distributed in the container 1a, the structure, material, etc. will not be limited. The size of the disperser is appropriately selected depending on the shape and size of the container 1a, the amount of carrier gas to be introduced, the thickness of the gas introduction pipe 2, and the like. For example, as the disperser, in addition to the baffle plate, a filter made of sintered metal or glass, a net, a honeycomb, a perforated pipe, or the like can be used. Among these, a sintered metal filter, a baffle plate, and a perforated pipe can be preferably used, and a baffle plate and a perforated pipe can be more preferably used.

  FIG. 5 shows an example of a supply device having a baffle plate 6 acting as a disperser. The baffle plate 6 is a member processed into a cone shape with a recessed central portion when viewed from the side where the carrier gas is introduced, and the recessed portion is formed below the gas inlet tube 2 as an outlet of the gas inlet tube 2. It is made to oppose and is arrange | positioned in parallel with the upper wall surface of the container 1a. Other configurations are the same as those described in the first embodiment, and the description thereof is omitted and the same reference numerals as those in FIG. In addition, although the figure showed the example which comprised the disperser with the cone-shaped baffle plate 6, the shape of the baffle plate 6 is not specifically limited, For example, a flat plate may be sufficient.

  In the supply apparatus configured as described above, the carrier gas introduced into the container 1a from the gas introduction pipe 2 collides with the baffle plate 6, whereby the carrier gas immediately after being introduced into the container 1a is contained in the container. Disperse within 1a.

  When the baffle plate 6 is used as a disperser, it is preferable to dispose the baffle plate 6 in parallel with the upper wall surface of the container 1a in order to favorably disperse the carrier gas introduced into the container 1a.

  On the other hand, when using a perforated pipe as a disperser, the perforated pipe may be arranged so that the hole formed in the perforated pipe faces a direction perpendicular to the upper wall surface of the container 1a. It is preferable when it is introduced in a well dispersed state.

  The number and size of the holes provided in the perforated pipe are not particularly limited. Also, the position of the hole is not particularly limited, but it is preferable that the hole is formed over the entire circumference of the pipe in order to more uniformly disperse the carrier gas in the container 1a. The disperser using the perforated pipe can be configured as a part of the gas introduction pipe 2 by making a plurality of holes on the peripheral surface of the gas introduction pipe 2. Alternatively, the perforated pipe may be formed of a member different from the gas introduction pipe 2 and connected to the tip of the gas introduction pipe 2. The carrier gas passes from the gas introduction pipe 2 through the perforated pipe, and is distributed and introduced into the container 1a from the hole provided on the peripheral surface thereof.

  As mentioned above, although this invention was demonstrated by showing the 1st-2nd embodiment, this invention is not limited to embodiment mentioned above, A various change is within the range of the technical idea of this invention. Can be added.

  For example, in the above-described embodiment, the example in which the two containers 1a and 1b are arranged apart from each other is shown, but they may be arranged in contact with each other. In the above-described embodiment, the example in which the two containers 1a and 1b are arranged in parallel has been described. However, the positional relationship is not particularly limited as long as the lower ends of the two containers 1a and 1b are connected to each other. .

  6A to 6F specifically show the appearance of an example of a supply device configured according to the present invention. 6A is a front view thereof, FIG. 6B is a rear view thereof, FIG. 6C is a right side view thereof, FIG. 6D is a left side view thereof, FIG. 6E is a plan view thereof, and FIG.

  The supply device shown in FIGS. 6A to 6E has two cylindrical containers 1a and 1b, and the container 1a to which the gas introduction pipe 2 for introducing the carrier gas is attached is for leading out the carrier gas. The capacity is larger than that of the container 1b to which the gas outlet pipe 3 is attached. In the container 1 a on the side where the carrier gas is introduced, the filling port 4 is provided separately from the gas introduction pipe 2. The insides of the two containers 1a and 1b communicate with each other through a communication pipe 5 connected to the lower ends of the containers 1a and 1b. The communication pipe 5 is configured by combining straight pipes. The gas introduction pipe 2 may be configured such that the carrier gas introduced into the container 1a collides with the upper wall surface of the container 1a inside the container 1a. Further, inside the container 1a, the gas introduction pipe 2 may be provided with a disperser for dispersing the carrier gas introduced into the container 1a.

  Next, the present invention will be specifically described with reference to examples, but the scope of the present invention is not limited thereto. The concentration of trimethylindium flowing out from the gas outlet tube 3 was measured with an ultrasonic gas concentration meter (trade name: Piezocon (manufactured by Lorex)).

Example 1
Trimethylindium was prepared as a solid organometallic compound at room temperature, and sponge titanium (particle size: 0.84 mm to 2.00 mm (manufactured by Toho Titanium)) was prepared as a carrier. In a stainless steel container with an internal volume of 1600 ml, 75 g of sponge titanium and 65 g of trimethylindium were placed, heated to 90 ° C. to completely melt the trimethylindium, and then cooled to room temperature to support the trimethylindium on the sponge titanium. . Next, this was crushed with a stainless steel tool such as a spatula and then sieved with a 4-mesh and 20-mesh sieve to obtain 126 g of trimethylindium carrying sponge titanium having a particle size of 0.84 to 4.76 mm.

  The obtained sponge titanium-supporting trimethylindium was filled from the filling port 4 as the organometallic compound 10 into two containers 1a and 1b of the supply device configured as shown in FIG. In this example, 126 g of tritium indium carrying sponge titanium having a total amount of trimethylindium of 50 g was filled in 96 g and 30 g in two containers 1a and 1b, respectively.

  As the supply device, the containers 1a and 1b are both cylindrical, and the size of the container 1a on the side into which the carrier gas is introduced has an inner diameter of 55 mm, a height of 135 mm, and an internal volume of 302 ml, and the carrier gas is derived. The side container 1b had a size of an inner diameter of 23 mm, a height of 135 mm, and an internal volume of 53 ml. Inside the container 1a, below the gas introduction pipe 2, a disperser 6 composed of a cone-shaped baffle plate having a recessed central portion is disposed. The communication pipe 5 and the disperser 6 were configured by combining straight pipes having an inner diameter of 4.3 mm. The containers 1a and 1b, the communication pipe 5 and the disperser 6 were made of stainless steel.

  After filling the sponge titanium-supporting trimethylindium, 100 ml of the dispersion material 11 was filled only in the container 1a on the side where the carrier gas was introduced. As the dispersion material 11, an alumina sphere (diameter: 0.5 mm) was used.

  The supply device is installed in a constant temperature bath maintained at 20 ° C. under normal pressure, and argon gas is introduced as a carrier gas from the gas introduction pipe 2 into the container 1 a at a flow rate of 1500 ml per minute, and is led out from the gas introduction pipe 3. A stable supply test of trimethylindium was performed by measuring the trimethylindium concentration in the gas over time. As a result, the supply amount of trimethylindium obtained from the gas outlet pipe 3 of the container 1b was about 0.95 g / hour, and the supply rate was stable up to a usage rate of 91%. Similarly, a stable supply test of trimethylindium was performed at an argon gas supply rate of 2000 ml / min. As a result, the trimethylindium supply rate obtained from the gas outlet tube 3 was about 1.30 g / hour, and the supply rate was It was stable up to a usage rate of 89%. FIG. 7 shows a graph of the relationship between the proportion of trimethylindium used and the supply amount obtained by the stable supply test of Example 1.

(Example 2)
In Example 1, 123 g of trimethylindium carrying sponge titanium having a total amount of trimethylindium of 50 g was filled in 92 g and 31 g in two containers 1a and 1b, respectively, and SUS balls (made of stainless steel) were used as the dispersion material 11. (Diameter: 2.0 mm) A stable supply test of trimethylindium was conducted in the same manner as in Example 1 except that 100 ml of the container 1a was filled.

  As a result, when the supply amount of argon gas was 1500 ml per minute, the supply amount of trimethylindium obtained from the gas outlet tube 3 was about 0.95 g per hour, and the supply rate was stable up to a usage rate of 89%. It was. When the supply amount of argon gas is 2000 ml / min, the supply amount of trimethylindium obtained from the gas outlet tube 3 is about 1.30 g / hour, and the supply rate is stable up to a usage rate of 88%. It was.

(Example 3)
In Example 1, the supply device having the structure shown in FIG. 1 was used as the supply device, and 128 g of trimethylindium carrying sponge titanium having a total amount of trimethylindium of 50 g was added to 97 g and 31 g in two containers 1a and 1b, respectively. A stable supply test of trimethylindium was performed in the same manner as in Example 1 except that the filling was performed separately.

  In the supply apparatus used in Example 3, the containers 1a and 1b are both cylindrical, and the size of the container 1a on the side where the carrier gas is introduced is 55 mm in inner diameter, 135 mm in height, and 302 ml in internal volume. The size of the container 1b on the side from which the carrier gas is derived was 17.5 mm in inner diameter, 135 mm in height, and 31 ml in internal volume.

  As a result of the stable supply test of trimethylindium, when the supply amount of argon gas is 1500 ml / min, the supply amount of trimethylindium obtained from the gas outlet tube 3 is about 0.95 g / hour, and the supply rate is 86%. The usage rate was stable. When the supply amount of argon gas is 2000 ml / min, the supply amount of trimethylindium obtained from the gas outlet tube 3 is about 1.30 g / hour, and the supply rate is stable up to a usage rate of 84%. It was.

Example 4
In Example 3, 110 g of alumina spheres (diameter: 0.5 mm) were used as a carrier for supporting trimethylindium, and 147 g of trimethylindium supporting alumina spheres having a total amount of trimethylindium of 50 g was placed in two containers 1a and 1b. A stable supply test of trimethylindium was carried out in the same manner as in Example 3 except that 108 g and 39 g were filled respectively.

  As a result, when the supply amount of argon gas was 1500 ml per minute, the supply amount of trimethylindium obtained from the gas outlet tube 3 was about 0.95 g / hour, and the supply rate was stable up to a usage rate of 85%. It was. When the supply amount of argon gas is 2000 ml / min, the supply amount of trimethylindium obtained from the gas outlet tube 3 is about 1.30 g / hour, and the supply rate is stable up to a usage rate of 81%. It was.

(Example 5)
In Example 1, 123 g of tritium indium carrying sponge titanium, in which the total amount of trimethylindium is 50 g, is filled into two containers 1a and 1b in 70 g and 53 g, respectively, using a supply device in which the size of the container 1a is changed. In addition, a stable supply test of trimethylindium was conducted in the same manner as in Example 1 except that 230 ml of alumina spheres were filled in the container 1a as the dispersion material 11. As for the size of the container 1a, the inner diameter was 83 mm, the height was 135 mm, and the internal volume was 690 ml.

  As a result of the stable supply test of trimethylindium, when the supply amount of argon gas is 1500 ml / min, the supply amount of trimethylindium obtained from the gas outlet tube 3 is about 0.95 g / hour, and the supply rate is 91%. The usage rate was stable. When the supply amount of argon gas is 2000 ml / min, the supply amount of trimethylindium obtained from the gas outlet tube 3 is about 1.30 g / hour, and the supply rate is stable up to a usage rate of 89%. It was.

(Example 6)
In Example 5, 128 g of trimethylindium supported on sponge titanium having a total amount of trimethylindium of 50 g was filled in two containers 1a and 1b in 75 g and 53 g, respectively, and 150 ml of alumina spheres were used as the dispersion material 11 in the container. A stable supply test of trimethylindium was performed in the same manner as in Example 1 except that 1a was filled. As for the size of the container 1a, the inner diameter was 83 mm, the height was 135 mm, and the internal volume was 690 ml.

  As a result of the stable supply test of trimethylindium, when the supply amount of argon gas is 1500 ml per minute, the supply amount of trimethylindium obtained from the gas outlet tube 3 is about 0.95 g / hour, and the supply rate is 90%. The usage rate was stable. When the supply amount of argon gas is 2000 ml / min, the supply amount of trimethylindium obtained from the gas outlet tube 3 is about 1.30 g / hour, and the supply rate is stable up to a usage rate of 88%. It was.

(Example 7)
In Example 6, trimethylindium having a total amount of trimethylindium of 330 g, trimethylindium supported on sponge titanium, was charged in the same manner as in Example 6 except that the two containers 1a and 1b were filled with 761 g and 56 g, respectively. A stable supply test was conducted. In Example 7, the stable supply test was performed only when the supply amount of argon gas was 1500 ml per minute.

  As a result of the stable supply test, the supply amount of trimethylindium obtained from the gas introduction pipe 3 was about 0.95 g per hour, and the supply rate was stable up to 90%.

(Comparative Example 1)
In Example 1, 123 g of tritium indium carrying sponge titanium, in which the total amount of trimethylindium is 50 g, is filled in 92 g and 31 g in two containers 1a and 1b, respectively, and the dispersion material is placed in the container 1a of the supply device A stable supply test of trimethylindium was carried out in the same manner as in Example 1 except that was not charged.

  As a result, when the supply amount of argon gas is 1500 ml per minute, the supply amount of trimethylindium obtained from the gas outlet tube 3 is about 0.95 g per hour, and the supply rate is stable up to a usage rate of 68%. I did not. Further, when the supply amount of argon gas is 2000 ml / min, the supply amount of trimethylindium obtained from the gas outlet tube 3 is about 1.30 g / hour, and the supply rate is stable only up to a usage rate of 65%. It wasn't. FIG. 8 shows a graph of the relationship between the use ratio of trimethylindium and the supply amount obtained by the stable supply test of Comparative Example 1.

  Table 1 summarizes main test conditions and test results of Examples 1 to 7 and Comparative Example 1 described above.

  From Table 1, in Comparative Example 1, the ratio of stable use of trimethylindium was 68% or less, whereas in Examples 1-7, 81% or more was achieved. It can be said that the usage rate was greatly improved.

It is typical sectional drawing of the supply apparatus of the organometallic compound by the 1st Embodiment of this invention. It is typical sectional drawing of the other example of the supply apparatus of the organometallic compound by the 1st Embodiment of this invention. It is typical sectional drawing of the other example of the supply apparatus of the organometallic compound by the 1st Embodiment of this invention. It is typical sectional drawing of the supply apparatus of the organometallic compound by the 2nd Embodiment of this invention. It is typical sectional drawing of the other example of the supply apparatus of the organometallic compound by the 2nd Embodiment of this invention. It is a front view which shows the external appearance of one specific example of the supply apparatus by this invention. It is a rear view of the supply apparatus shown to FIG. 6A. It is a right view of the supply apparatus shown to FIG. 6A. It is a left view of the supply apparatus shown to FIG. 6A. It is a top view of the supply apparatus shown to FIG. 6A. It is a bottom view of the supply apparatus shown to FIG. 6A. 4 is a graph showing the relationship between the usage ratio of trimethylindium and the supply amount obtained by the stable supply test of Example 1. 3 is a graph showing the relationship between the usage rate of trimethylindium and the supply amount obtained by the stable supply test of Comparative Example 1. It is typical sectional drawing of the conventional supply apparatus.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1a, 1b Container 2 Gas introduction pipe 3 Gas outlet pipe 4 Filling port 5 Communication pipe 6 Dispersor 10 Organometallic compound 11 Dispersant

Claims (9)

A supply device for supplying an organometallic compound that is solid at room temperature with a carrier gas,
A column-type first container provided with a carrier gas inlet at the top;
A column-type second container provided with an outlet for the carrier gas at the top;
A communication member that is disposed below the first container and the second container and communicates the inside of the first container and the inside of the second container at its lower end;
Have
The first container is filled with a dispersion material for dispersing the organometallic compound and the carrier gas introduced from the introduction port in this order from the bottom of the first container, and the second container Is filled with the organometallic compound. The supply device according to claim 1, wherein the second container is not filled with the dispersion material. The dispersed material is feeding device according to claim 1 or 2, wherein in the first container covering the organometallic compound is filled in layers. The supply device according to any one of claims 1 to 3, wherein the dispersion material is an aggregate of a large number of members and has a gap between the members. The supply device according to claim 4 , wherein the member is spherical. The said introduction port is equipped with the gas introduction pipe | tube attached to the said 1st container so that the carrier gas introduced into the said 1st container collides with the upper wall surface of the said 1st container. The supply device according to any one of 1 to 5 . The supply device according to any one of claims 1 to 5 , wherein the introduction port includes a disperser that disperses the carrier gas introduced into the first container. The supply device according to claim 1, wherein a ratio of a capacity of the second container to a capacity of the first container is 1 to 80. The supply container according to any one of claims 1 to 8, wherein a ratio of a height to a diameter of the internal dimensions of the first and second containers is 0.8 to 10.0.

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