JP5257197B2 - Organometallic compound feeder - Google Patents

Description

  The present invention relates to an apparatus for supplying an organometallic compound. Specifically, a carrier gas is supplied to an apparatus containing a solid organometallic compound at normal temperature, preferably at normal temperature and normal pressure, to prepare a carrier gas containing the organometallic compound at a more stable concentration, and the organometallic compound is used. Organometallic compound that supplies the carrier gas prepared in the apparatus and prepares the carrier gas using the organometallic compound contained in the apparatus at a higher rate, that is, can be prepared at a higher usage rate. It relates to a supply device.

  Organometallic compounds are used as raw materials in the epitaxial growth of compound semiconductors. In particular, it is often used in a metal organic chemical vapor deposition method (MOCVD method) excellent in mass productivity and controllability.

  For example, trimethylgallium and trimethylaluminum, which are liquid organometallic compounds at room temperature, and trimethylindium, which is a solid organometallic compound at room temperature, are used for high mobility electronic devices, high-intensity optical devices, high-capacity optical communication lasers, It has been used as a raw material in an element used in a density recording laser or the like. Another example in which a solid organometallic compound is used at room temperature is a case where biscyclopentadienylmagnesium used as a p-type dopant of gallium nitride is used when a blue light emitting device is manufactured.

  The organometallic compound is filled in a filling container, and by flowing a carrier gas thereto, the organometallic compound in contact with the carrier gas is taken into the carrier gas as a vapor, and is taken out of the filling container along with the carrier gas. It is supplied to a vapor phase growth apparatus or the like.

  As such a filling container, a cylindrical one made of stainless steel is usually used. In order to improve the thermal efficiency, the controllability of the concentration of the organometallic compound in the carrier gas, the usage rate, etc., the structure of the bottom of the container is used. Filling containers having various characteristics in a carrier gas introduction pipe and the like are known. Further, from the viewpoint of improving productivity, larger filling apparatuses have been used.

  For organometallic compounds that are liquid at room temperature, such as trimethylgallium and trimethylaluminum, contact between the carrier gas and the organometallic compound occurs easily by bubbling the carrier gas into the organometallic compound, and the organometallic compound is the carrier. Accompanied by gas and taken out of the filling container. Since the organometallic compound that is liquid at room temperature easily flows and moves to the bottom of the filling container in the filling container, bubbling is reliably performed even when the remaining amount of the organometallic compound in the filling container is low, which is efficient. (See FIG. 1).

  On the other hand, when an organometallic compound that is solid at room temperature such as trimethylindium is filled as it is, the organometallic compound in the portion in direct contact with the carrier gas is consumed preferentially over the organometallic compound in the other portion. That is, it is taken in the carrier gas. Since the solid organometallic compound has poor fluidity, once partial consumption starts, the consumption of the portion is continuously promoted to form a channel through which the carrier gas easily flows. When such a flow path is formed, the contact area between the carrier gas and the organometallic compound decreases, and the concentration of the organometallic compound in the carrier gas derived from the filling container gradually decreases. As a result, the organometallic compound cannot be stably supplied to a reaction furnace such as an MOCVD apparatus.

  Usually, when the concentration of the organic compound in the carrier gas decreases, the use of the organometallic compound is stopped, so that the solid organometallic compound that has not been consumed remains in the filling container as shown in FIG. . Therefore, when a solid organometallic compound is filled as it is at normal temperature, a carrier gas containing the organometallic compound in a stable concentration cannot be obtained for a long time, and the organometallic compound is not used efficiently.

  If the usage rate of the solid organometallic compound remaining in the filled container is low, the productivity is lowered, which is not preferable. Therefore, a carrier gas containing a solid organometallic compound filled in a container at a stable concentration can be supplied, and in order to use the organometallic compound efficiently, the carrier gas is uniform in the solid organometallic compound filled in the container. Various measures have been taken to make it flow into

  For example, as a method of dispersing the carrier gas in the initial stage of introducing the container, a method using a diffuser (see Patent Document 1), a method of arranging a filler on a solid organometallic compound (see Patent Document 2), and a carrier gas with a central axis of the container For example, a method (see Patent Document 3) that introduces substantially perpendicular to the above has been introduced.

  Further, as a method of flowing the carrier gas uniformly in the solid organometallic compound and making the contact with the carrier gas efficient, the solid organometallic compound supported on the inert carrier is filled in the filling container, A method of flowing a carrier gas downward from the bottom (see FIG. 3) (see Patent Document 4), a method of filling a solid organometallic compound together with a filler (see Patent Document 5), and the like have been proposed. By the method as described above, the solid organometallic compound is uniformly consumed at the initial introduction portion of the carrier gas.

  On the other hand, as a method for deriving the carrier gas, a container in which the tip of the carrier gas deriving tube is disposed in a solid organometallic compound (see Patent Document 4), and a method using a porous element in the carrier gas deriving port (Patent Document 2, Patent Document 6) has been proposed.

  However, there are various problems as a method for deriving the carrier gas. Consumption of the solid organometallic compound progresses sequentially from the vicinity of the carrier gas introduction port, and as the consumption progresses, there is a problem that the consumption becomes non-uniform due to the distribution of the flow velocity in the vicinity of the portion where the carrier gas is derived.

  For example, in a method such as using a carrier gas outlet pipe, the carrier gas concentrates at the tip of the outlet pipe at the bottom of the filling container, and the carrier gas flow velocity is near the bottom wall surface of the filling container and near the carrier gas outlet. The difference becomes larger. Therefore, the solid organometallic compound is preferentially consumed at the periphery of the tip of the carrier gas outlet tube over the vicinity of the wall surface of the bottom of the filling container, and a sufficient amount of the solid organometallic compound is present at the periphery of the tip of the carrier gas outlet tube. If no longer exists, the concentration of the solid organometallic compound in the derived carrier gas decreases. As a result, a gas containing an organometallic compound at a desired concentration cannot be stably supplied to a reactor such as an MOCVD apparatus even though the solid organometallic compound remains in the container.

  To increase the consumption of organometallic compounds by increasing the size of reactors such as MOCVD equipment, for the purpose of increasing the size of containers filled with solid organometallic compounds and further increasing the supply per unit time, This problem becomes more noticeable when the amount of carrier gas introduced into the filling container is increased. That is, it becomes more difficult to derive a carrier gas containing an organometallic compound at a stable concentration over a long period of time and to efficiently consume the solid organometallic compound remaining in the filled container.

  As a method for solving the problem at the time of deriving the carrier gas, a filled container using a sintered metal filter or a perforated plate has been proposed (see Patent Document 7). However, when the sintered metal or perforated plate is small, clogging occurs due to the solid organometallic compound, the carrier gas flowing in the solid organometallic compound drifts, and the solid organometallic compound is consumed unevenly. It is thought to be a cause.

Japanese Unexamined Patent Publication No. 02-124796 JP 2007-314878 Japanese Patent Application No. 2007-225595 Japanese Unexamined Patent Publication No. 1-265511 Japanese Patent Publication No. 5-39915 JP 2002-83777 A JP 2006-161162 A

  An object of the present invention is to prepare a carrier gas containing an organometallic compound, in particular, an organometallic compound that is solid at room temperature at a more stable concentration, and supply it to another apparatus (for example, an organometallic vapor phase growth apparatus) to fill the solid An object of the present invention is to provide an organometallic compound supply apparatus capable of increasing the usage rate of an organometallic compound.

As a result of intensive investigations on an apparatus for supplying a solid organometallic compound at room temperature, particularly at room temperature and normal pressure,
A filled container containing an organometallic compound supported on an inert carrier;
A support plate that holds the organometallic compound in a filled container, particularly in the lower part thereof, and through which a carrier gas can pass;
A carrier gas inlet located at the top of the filling container;
A carrier gas outlet opening located at the bottom of the filling container and opened below the support plate; and a baffle plate larger than the carrier gas outlet opening provided between the support plate and the carrier gas outlet port. An organometallic compound supply apparatus comprising a carrier gas introduced from a carrier gas inlet into a filling container and passing through an organometallic compound held on a support plate from above to below. The present inventors have found that a solid organometallic compound can be effectively used by using an organometallic compound supply device discharged from the outlet, and have reached the present invention.

Accordingly, the present invention provides an organometallic compound supply apparatus comprising a filling container that is filled with a solid organometallic compound at room temperature, and that supplies a carrier gas to sublimate the organometallic compound.
A support plate (9) for holding the organometallic compound (8) supported on an inert carrier in the filling container (1) and allowing a carrier gas to pass through;
A carrier gas inlet (4) at the top of the filling container;
A carrier gas outlet (5) which is the bottom of the filling container and opens below the support plate, and the carrier attached between the support plate (9) and the carrier gas outlet (5) Baffle plate (10) larger than the diameter of the gas outlet (5)
And an organic metal compound supply device characterized in that the organic metal compound carried on an inert carrier filled with a carrier gas on a support plate is passed from above to below. .

  By using the supply device of the present invention, an organometallic compound that is solid at room temperature can be supplied with a more stable concentration along with the carrier gas, and the usage rate of the organometallic compound filled in the filling container can be further increased. .

It is a cross-sectional schematic diagram of the filling container filled with the liquid organometallic compound. It is a cross-sectional schematic diagram of the filling container filled with the solid organometallic compound. It is a cross-sectional schematic diagram of the filling container filled with the solid organometallic compound carry | supported by the conventional inert support | carrier. It is a cross-sectional schematic diagram of one aspect of the organometallic compound supply apparatus of this invention which has a filling container filled with the solid organometallic compound carry | supported by the inert support | carrier. FIG. 5 is a schematic cross-sectional view of another embodiment of the organometallic compound supply apparatus of the present invention having a filling container filled with a solid organometallic compound supported on an inert carrier. It is a plane schematic diagram of an example of a support plate ((a) wire mesh-like support plate, (b) eye plate-like support plate). 3 is a graph showing the results in Example 1. It is a graph which shows the result in Example 2. 10 is a graph showing results in Example 3. It is a graph which shows the result in a comparative example. It is a graph which shows the influence which the baffle plate size has on the effect. It is a cross-sectional schematic diagram which shows the other aspect of a baffle plate ((a) conical baffle plate, (b) reverse conical baffle plate, (c) baffle plate which attached the semicircle plate in steps).

  The solid organometallic compound filled in the supply device of the present invention is useful as a raw material for a compound semiconductor by a vapor phase growth method, for example, and is solid at room temperature, particularly at room temperature and normal pressure. Examples include: indium compounds such as trimethylindium, dimethylchloroindium, cyclopentadienylindium, trimethylindium / trimethylarsine adduct, trimethylindium / trimethylphosphine adduct; ethyl zinc iodide, ethylcyclopentadienylzinc, Zinc compounds such as cyclopentadienyl zinc; aluminum compounds such as methyldichloroaluminum; gallium compounds such as methyldichlorogallium, dimethylchlorogallium and dimethylbromogallium; biscyclopentadienylmagnesium and the like.

  In addition, the carrier for supporting such an organometallic compound is not particularly limited as long as it is inert to the solid organometallic compound. For example, the following can be used: alumina, silica, mullite, glassy carbon, graphite, potassium titanate, quartz, silicon nitride, boron nitride, silicon carbide and other ceramics, stainless steel, aluminum, nickel, tungsten and other metals, Fluororesin, glass, etc. The shape of the carrier is not particularly limited, and may be various shapes such as an indefinite shape, a spherical shape, a fiber shape, a net shape, a coil shape, a circular tube shape, and the like. The carrier preferably has fine irregularities with a size of about 100 to 2000 μm, or has a large number of pores (voids) in the carrier itself, rather than a smooth surface. Examples of such carriers include alumina balls, Raschig rings, Helipac, Dickson packing, stainless sintered elements, glass wool, metal wool and the like.

  Examples of the support plate include a wire mesh shape and a mesh plate shape as shown in FIG. The support plate has an opening for the outlet tube at the center. The size of the opening of the support plate is not limited so long as the carrier does not fall, and usually about 1 to 5 mm, preferably about 1.5 to 3 mm is used. The shape of the opening is not particularly limited, and examples thereof include a polygonal shape, a circular shape, and an elliptical shape. The material of the support plate is not particularly limited as long as it is inert with respect to the solid organometallic compound. For example, glass, metal, ceramic, etc. can be used, but from the viewpoint of thermal conductivity, metal Those made of stainless steel are preferable, and those made of stainless steel are particularly preferable.

  On the other hand, a sintered metal filter can be used as the support plate. However, if the sintered metal has an excessively small mesh size, there is a possibility that the pressure loss is large or that the carrier gas drifts.

  In the organometallic compound supply device of the present invention, the carrier gas inlet and the carrier gas outlet mean the inlet of the carrier gas into the filling container and the outlet of the carrier gas from the inside of the filling container, respectively. In one preferable aspect, the carrier gas introduction port and the carrier gas outlet port serve as an outlet tube for discharging the carrier gas from the opening and an opening portion at the end of a pipe as an introduction tube for supplying the carrier gas to the filling vessel, respectively. It is an opening part in the edge part of piping. Normally, such gas piping is a tube having a circular cross section, and in this case, the shape of the inlet and outlet is also circular. Of course, the inlet and the outlet may have different shapes, and correspondingly, the pipe through which the carrier gas flows may have a different cross section. In another aspect, the inlet and the outlet may be openings provided directly in the filling container.

  In the organometallic compound supply apparatus of the present invention, the baffle plate is a plate positioned between the support plate and the carrier gas outlet. As a result, does the entire carrier gas flow (substantially vertically downward or close to it) that passes through the region of the organometallic compound located immediately above the baffle plate collide with the baffle plate? Or, in order to collide, the flow direction of such carrier gas is changed to another direction by the baffle plate. For example, it flows in a flow direction that is not vertically downward. More specifically, it flows in a direction toward the side wall of the filling container (for example, horizontally or obliquely downward). Thereafter, such carrier gas flows around the peripheral portion of the baffle plate and flows toward the carrier gas outlet located below the baffle plate.

  In order to prevent the carrier gas flow rate from increasing due to the concentration of the carrier gas around the carrier gas outlet, it is effective to increase the outlet by increasing the diameter of the pipe through which the carrier gas flows. Note that when a large flow rate of carrier gas is flowed, the filled solid organometallic compound may be discharged out of the container through the pipe as a solid. It is preferable to make it moderately small without increasing it. In general, the carrier gas outlet pipe uses a pipe having an outer diameter of about 10 mm or less. However, by attaching a baffle plate larger than the pipe diameter, the carrier gas is led out from the filling container around the baffle plate. As a result, more carrier gas flows also in the peripheral part of the side wall of the filling container, and the carrier gas concentrates directly on the tip part of the carrier gas outlet pipe without passing through the peripheral part of the side wall of the filling container. Can be suppressed.

  In the present specification, the shape and size of the baffle plate are the normal projection of a structure configured as a baffle plate below the support plate onto a plane perpendicular to the length direction (and hence the vertical direction) of the body of the filling container. It means the shape and size of things. If the normal projection of the baffle plate is superimposed on the normal projection of the carrier gas outlet, the normal projection of the baffle plate covers all of the normal projection of the outlet, and from the periphery of the normal projection of the carrier gas outlet. Preferably, the baffle plate has a shape and size having a portion extending outward. In the present invention, the description “a baffle plate that is larger than the diameter of the carrier gas outlet” is used in this sense. In the present invention, generally, the effect of the baffle plate is that the figure obtained when the baffle plate is normally projected in a direction perpendicular to the longitudinal direction (or vertical direction) of the container body is similarly derived from the outlet port. Is obtained by covering and extending outwardly the figure obtained in the case of normal projection. Therefore, as shown in FIG. 12, the baffle plate does not necessarily have to be perpendicular to the longitudinal direction of the filling container body and extend on the same plane, for example, oblique with respect to the longitudinal direction, or It may be attached in steps.

  As described above, even if the baffle plate is attached around the carrier gas outlet pipe (that is, as shown in FIG. 4 described later, the outlet pipe penetrates the baffle plate). It is possible to suppress the carrier gas from directly concentrating on the tip portion of the carrier gas outlet pipe without passing through the peripheral portion of the side wall of the filling container. In this embodiment, the shape and size of the baffle plate mean the shape and size of the baffle plate when it is assumed that the lead-out tube does not exist (that is, the lead-out tube does not penetrate the baffle plate).

  When the size of the baffle plate becomes excessively large and approaches the diameter of the filling container body, the carrier gas concentrates on the periphery of the side wall at the bottom of the filling container, and the carrier gas flows around the carrier gas outlet pipe above the baffle plate. It becomes difficult to flow, and consumption of the solid organometallic compound located above the baffle plate hardly occurs. Therefore, it is recommended that the baffle has a diameter of about 10% to 75%, preferably about 20% to 60%, with respect to the inner diameter of the filling container. If the shape of the baffle plate and the cross section of the filling container are not circular, the diameter of the baffle plate and the inner diameter of the filling container are based on the hydraulic equivalent diameter.

  The material of the baffle plate is not particularly limited as long as it is inert to the solid organometallic compound, and glass, metal, ceramic, etc. can be used, but from the viewpoint of thermal conductivity, it is made of metal. In particular, those made of stainless steel are preferred. The shape of the baffle plate is not particularly limited, and examples thereof include a polygonal shape, a circular shape, and an elliptical shape, but a circular shape is particularly preferable from the viewpoint of symmetry.

  It is preferable that the baffle plate is located farther from the solid organometallic compound than in the solid organometallic compound. This is because when the baffle plate is above the support plate or at the same position as the support plate, the flow of the carrier gas is likely to be cut off directly above the baffle plate, resulting in consumption of the solid organometallic compound. It is difficult. On the other hand, when the position of the baffle plate is lower than the support plate, there is no solid organometallic compound in the region where the flow of the carrier gas just above the baffle plate is easily blocked, so the region where the solid organometallic compound is hardly consumed is formed. Can be small.

  Further, the horizontal circular cross section of the height (or level) filling container to which the baffle plate, the carrier gas outlet and the baffle plate are attached is substantially concentric, that is, their centers are located on substantially the same vertical line. It is preferable to do. Even if it is not concentric, a certain degree of effect can be obtained, but the concentricity allows the carrier gas to flow symmetrically in the filling container, so that the solid organometallic compound is consumed evenly, and the usage rate of the solid organometallic compound Can be made higher.

  As a method for supporting a solid organometallic compound on an inert carrier, any of the conventional methods may be used. For example, a method in which a support and a solid organometallic compound are put in a rotating container in accordance with a predetermined weight ratio, and then this is heated to melt the solid organometallic compound, and then slowly cooled with rotary stirring, solid organic For example, a method in which the support is introduced into the metal compound while being heated and melted, and then the excess melted organometallic compound is taken out and then slowly cooled is employed.

  In carrying the carrier, it is important to remove oxygen, moisture and other volatile impurities contained in the carrier in advance. If oxygen or moisture is present on the surface of the carrier, the solid material may be altered or contaminated, so when used as a raw material for vapor phase growth, not only the quality of the resulting film is impaired, It will not be possible to stably supply the original raw material. In order to avoid such inconvenience, the carrier should be vacuum degassed in advance while being heated at an acceptable temperature of the material, and then the voids should be replaced with an inert gas such as nitrogen or argon. Is recommended.

  The solid organometallic compound supported on the carrier is usually in the range of about 10 to 100 parts by weight, preferably about 30 to 70 parts by weight with respect to 100 parts by weight of the carrier. When about 10 parts by weight or less is loaded, the amount of the solid organometallic compound occupying the volume of the filled container is small, so the container must be made larger than necessary, and is often not economical. Further, when about 100 parts by weight or more is supported, the effect is often not sufficiently obtained because the surface area of the solid organometallic compound per filling volume does not increase as expected.

  FIG. 4 shows an embodiment of an organometallic compound supply apparatus comprising a filling container 1 filled with a solid organometallic compound of the present invention. A support plate 9 that holds the organometallic compound 8 supported on the inert carrier and allows the carrier gas to pass therethrough is disposed below the filling container 1 having a curved bottom. A carrier gas introduction pipe 2 and a carrier gas outlet pipe 3 are connected to the upper part of the filling container. The carrier gas inlet 4 is open above the filling vessel 1 and above the organometallic compound 8 supported on the filled inert carrier, and the carrier gas outlet tube 3 passes through the inside of the filling vessel 1. The gas outlet 5 is open at the bottom of the filling container 1 and below the support plate 9.

  In the illustrated embodiment, the baffle plate 10 is attached above the carrier gas outlet 5, but the baffle plate 10 is located at the same level as the carrier gas outlet 5 (with respect to the vertical direction of the filling container 1). Even so, the baffle plate 10 can be changed around the baffle plate by changing the flow direction of the carrier gas descending toward it. Accordingly, even in this case, those skilled in the art can easily understand that the effects of the present invention described above can be achieved. Therefore, in the supply device of the present invention, the baffle plate may be positioned at substantially the same level as the carrier gas outlet, and the description “between the support plate and the carrier gas outlet” It includes both an aspect located at a level above the gas outlet and an aspect located at the same level as the carrier gas outlet. In the embodiment shown in FIG. 4, the baffle plate extends from the outer wall of the carrier gas outlet tube toward the side wall of the filling container (for example, a portion corresponding to the outer shape of the carrier gas outlet tube from a circular shape at the center). As a cut (or donut) shape.

  In the illustrated embodiment, the carrier gas outlet pipe 3 passes through the inside of the filling container 1, but the present invention is not limited to this, and the outlet port 5 opens at the bottom of the filling container 1 below the support plate 9. If so, the carrier gas outlet pipe may be disposed outside the filling container 1.

  FIG. 5 shows an embodiment of an organometallic compound supply apparatus comprising a filled container filled with a solid organometallic compound according to another embodiment of the present invention.

  A support plate 9 that holds the organometallic compound 8 supported on the inert carrier and allows the carrier gas to pass therethrough is disposed below the filling container 1 having a curved bottom. A carrier gas introduction pipe 2 is connected to the upper part of the filling container 1. The carrier gas inlet 4 is opened above the filling container 1 and above the organometallic compound 8 supported on the filled inert carrier. The carrier gas outlet pipe 3 is disposed outside the filling container 1, and the carrier gas outlet 5 is open at the bottom of the filling container 1 and below the support plate 9. A baffle plate 10 is attached to the upper part of the carrier gas outlet 5.

  In the embodiment of FIG. 5, the carrier gas outlet pipe 3 is disposed outside the filling container 1, but the present invention is not limited to this, and the outlet port opens at the bottom of the filling container below the support plate. If so, the carrier gas outlet pipe may be arranged inside the filling container 1.

  A desired amount of the solid organometallic compound 8 supported on the inert carrier is supplied into the filling container 1 from a supply port (not shown) and filled on the support plate 9. Note that the solid organometallic compound may be supported on an inert carrier in the filling container 1 as described above.

  The carrier gas introduction pipe 2 is connected to a carrier gas supply source, a flow rate control device (not shown), etc., and the carrier gas lead-out pipe 3 is connected to a gas concentration meter, a vapor phase growth apparatus (not shown), etc. For example, the filling container 1 is used in a thermostat.

  A carrier gas such as hydrogen gas is supplied from the carrier gas introduction pipe 2 to the filling container 1 at a predetermined flow rate, and the carrier gas passes through the carrier gas introduction port 4 while removing the gap between the organometallic compounds 8 supported on the inert carrier. By passing from above 1 downward, a carrier gas containing an organometallic compound is supplied from the carrier gas outlet 5 to the vapor phase growth apparatus or the like via the carrier gas outlet 3.

  4 and 5 show a curved bottom of the filling container 1, it is of course possible to use a filling container having a horizontal bottom. Further, the filling amount of the organometallic compound 8 supported on the inert carrier 1 into the filling container 1 (for example, the filling height, ie, the level in the vertical direction of the filling container) is usually lower than the level of the carrier gas inlet 4. As a target. However, this is not the case when the carrier gas inlet 4 is divided so that the carrier gas can be uniformly introduced above the organometallic compound 8 supported on the inert carrier. For example, when the carrier gas can be uniformly distributed and supplied as in the case where a carrier plate or a showerhead-like carrier gas inlet is used, the level of the carrier gas inlet 4 and the upper end level of the filled organometallic compound 8 are Almost the same.

  The organometallic compound supply apparatus of the present invention is suitable as an apparatus for supplying raw materials for vapor phase growth and the like.

  Examples of the present invention will be described below, but the present invention is not limited thereto.

Example 1
The baffle plate constituted the organometallic compound supply apparatus of the present invention similar to that of FIG. 4 except that the baffle plate was attached to the tip of the outlet tube, that is, the level of the outlet. The bottom of the filling container 1 is curved and has a volume of about 1300 cm ³ (inner diameter: 108 mm, depth: 147 mm), and a support plate 9 (opening size: 2 mm wire mesh) at a position 26 mm from the bottom of the filling container. )). A dispersion plate 11 (circular flat plate: diameter 18 mm) is attached to the carrier gas inlet 4 so that the distance between the container top plate and the dispersion plate 11 is 3 mm horizontally with the top plate of the filling container 1. It can be introduced substantially perpendicular to the central axis. Further, a baffle plate 10 (circular flat plate: 30 mm in diameter, provided that the carrier gas outlet port 5) of the carrier gas outlet tube 3 (outer diameter 8 mm, inner diameter 6 mm) opened at a position 10 mm below the support plate 9 is provided. The lead-out pipe penetrated through the center).

  This filled container 1 was filled with 585 g of alumina spheres having an average particle diameter (diameter) of 4.5 mm and 300 g of trimethylindium (hereinafter referred to as TMI) as inert carriers. The filled container 1 was heated to about 110 ° C. to melt the TMI in the filled container 1, and then gradually cooled to room temperature while rotating and stirring, so that the TMI was supported on alumina spheres.

About 900 cm ³ / min of hydrogen gas from the introduction pipe 2 as a carrier gas to the filling container 1 at a substantially constant speed (converted to atmospheric pressure, flow rate per unit area of the filling portion: about 9.5 cm ³ / cm ² · min ), The charged TMI was supplied so as to pass from the upper side to the lower side, and hydrogen gas containing TMI was taken out from the carrier gas outlet tube 3 through the carrier gas outlet port 5. The TMI with the carrier gas, hydrogen gas, was derived from the filling container 1, and the pressure inside the filling container 1 was set to 40 kPa (absolute pressure), and the filling container 1 was placed in a constant temperature bath and maintained at 25 ° C. .

  The TMI concentration in the hydrogen gas from the filling container 1 was measured using an epison concentration meter (manufactured by Thomas Swan Scientific Equipment Co., Ltd.) as a gas concentration meter. The TMI concentration was measured periodically, and the TMI usage rate (%) was determined from the hydrogen gas flow rate and the TMI concentration. The results are shown in FIG. The concentration of TMI was stable until the usage rate was about 87% and then decreased.

(Example 2)
A filling container 1 similar to that of Example 1 is different from that of Example 1 except that the diameter of the baffle plate 10 (circular flat plate) attached to the distal end portion (carrier gas outlet 5) of the carrier gas outlet tube 3 is 50 mm. Similarly, TMI was supported on alumina spheres.

The usage rate (%) of TMI was determined in the same manner as in Example 1. The results are shown in FIG.
The concentration of TMI was stable until the usage rate was about 87% and then decreased.

(Example 3)
In the same manner as in Example 1, except that the baffle plate 10 (circular flat plate) attached to the tip of the carrier gas outlet tube 3 (carrier gas outlet 5) has a diameter of 80 mm. TMI was supported on alumina spheres.

  The usage rate (%) of TMI was determined in the same manner as in Example 1. The results are shown in FIG. The concentration of TMI was stable until the usage rate was about 85%, and then decreased.

(Comparative Example 1)
TMI is applied to the same filling container 1 as in Example 1 except that the baffle plate 10 (circular flat plate) is not attached to the distal end portion (carrier gas outlet 5) of the carrier gas outlet pipe 3. It was supported on an alumina sphere.

  The usage rate (%) of TMI was determined in the same manner as in Example 1. The results are shown in FIG. The concentration of TMI was stable until the usage rate reached about 83%, and then decreased. In addition, the usage rate of TMI by the difference in baffle plate size with respect to the internal diameter of a filling container is shown in FIG.

DESCRIPTION OF SYMBOLS 1 Filling container 2 Carrier gas inlet tube 3 Carrier gas outlet 4 Carrier gas inlet 5 Carrier gas outlet 6 Liquid organometallic compound 7 Solid organometallic compound 8 Solid organometallic compound 9 supported on an inert carrier 9 Support plate 10 Baffle plate 11 Dispersion plate

Claims (5)

An organometallic compound supply apparatus comprising a filling container that is filled with a solid organometallic compound at room temperature and that sublimates the organometallic compound by supplying a carrier gas,
A support plate that holds the organometallic compound supported on an inert carrier in the filled container and through which a carrier gas can pass;
A carrier gas inlet at the top of the filling container;
A carrier gas outlet opening at the bottom of the filling container and opened below the support plate, and a diameter larger than the diameter of the carrier gas outlet port installed between the support plate and the carrier gas outlet port. An organometallic compound supply characterized in that it further comprises a baffle plate and passes through the organometallic compound supported on an inert carrier filled with a carrier gas on the support plate from above to below. apparatus.   The organometallic compound supply apparatus according to claim 1, wherein the support plate is a stainless steel wire mesh having a mesh size of 1 to 5 mm.   3. The organometallic compound supply apparatus according to claim 1, wherein the baffle plate larger than the diameter of the carrier gas outlet is a circular flat plate, and is arranged so as to be substantially concentric with the support plate and the body of the filling container. .   The carrier gas introduction port is configured such that the carrier gas supplied from the carrier gas introduction port is jetted substantially perpendicular to the central axis when the filling container is installed vertically. The organometallic compound supply apparatus according to 1.   The organometallic compound supply apparatus according to claim 1, wherein the organometallic compound is trimethylindium.

Images