JP2007053186A - Organic metal compound supplying vessel - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an organic metal compound supplying vessel for attaining quantity of vaporization of an organic metal compound having a constant reproducibility, and for reducing drop of usage of the organic metal compound as a filler when quantity of vaporization of the organic metal compound by increasing a flow rate of the carrier gas. <P>SOLUTION: In the organic metal compound supplying vessel, an end of a carrier gas introducing pipe is provided at the upper part of the vessel, an end part of the carrier gas exhausting pipe is provided at the bottom thereof, and the vessel is filled with a carrier supporting organic metal compound in which the carrier which is inactive to the organic metal compound is covered with the organic metal compound in the solid state under the normal temperature. The end of the carrier gas introducing pipe is specifically arranged with inclination of 20 to 50° in the diagonal lower direction for the horizontal direction. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an organometallic compound supply container. More specifically, the present invention relates to an organometallic compound supply container filled with a carrier-supporting organometallic compound obtained by coating an organometallic compound that is solid at room temperature with an inert carrier.

  Organometallic compounds are used, for example, as raw materials for compound semiconductors in the electronic industry. When an organometallic compound is used in the electronics industry, a carrier gas such as hydrogen gas is usually blown in contact with the organometallic compound and used as a saturated vapor of the organometallic compound and led to a vapor phase growth apparatus or the like.

  In the case of an organometallic compound that is solid at room temperature (room temperature), unlike a liquid, a flow path through which the carrier gas passes is formed in the laminated organometallic compound even when a carrier gas is blown, or small particles are formed by vaporization. As a result, the solid organometallic compound having a diameter is deposited on the bottom of the container, and as a result, sufficient contact between the solid organometallic compound and the carrier gas cannot be obtained, and the organometallic compound having a stable concentration cannot be supplied to the vapor phase growth apparatus. Has the disadvantages.

  For such organometallic compounds that are solid at room temperature, the tip of the carrier gas inlet tube is arranged vertically at the top of the container and the carrier gas at the bottom as a container that provides a certain reproducible amount of evaporation of the organometallic compound. Organometallic compound supply container for vapor phase growth in which the tip of the outlet tube is disposed and the container is filled with a carrier-supporting organometallic compound coated with an organometallic compound on a carrier inert to the organometallic compound Is known (see Patent Document 1).

However, although the supply container described in Patent Document 1 can obtain a certain reproducible amount of evaporation of the organometallic compound, the carrier gas flow rate is increased to increase the vaporization amount of the organometallic compound in order to increase the efficiency of vapor phase growth. If the number is increased, the usage rate of the filled organometallic compound decreases, that is, there is a problem that the organometallic compound remaining in the supply container increases at the time when the organometallic compound-containing gas with a certain concentration cannot be obtained. . The organometallic compound remaining in the supply container is taken out, the inside of the container is washed, and the container is reused.
JP-A-1-265511

  The object of the present invention is to obtain a certain reproducible amount of evaporation of the organometallic compound, and when the carrier gas flow rate is increased to increase the amount of evaporation of the organometallic compound, the use rate of the filled organometallic compound is reduced. It is an object to provide an organometallic compound supply container that can reduce the amount of water.

  As a result of diligent investigations to solve such problems, the present inventor has provided the tip of the carrier gas inlet pipe inclined at 20 to 50 ° obliquely downward with respect to the horizontal direction at the top of the container and the carrier gas outlet pipe at the bottom. Using a container provided with a tip, the inside of the container is filled with a carrier-supporting organometallic compound coated with a solid organometallic compound at room temperature on a carrier inert to the organometallic compound, and the tip of the carrier gas introduction pipe By introducing the carrier gas from the carrier gas and taking out the carrier gas containing the organometallic compound vaporized from the carrier gas outlet tube, a certain reproducible amount of organometallic compound evaporation is obtained, and the carrier gas flow rate is increased to increase the organic gas content. The inventors have found that when the amount of vaporization of the metal compound is increased, the decrease in the usage rate of the filled organometallic compound can be reduced, and the present invention has been achieved.

  That is, the present invention is arranged such that the top of the carrier gas inlet pipe is disposed at the top of the container, the tip of the carrier gas outlet pipe is disposed at the bottom, and the carrier inert to the organometallic compound is solid at room temperature. In an organometallic compound supply container filled with a carrier-supporting organometallic compound coated with an organometallic compound, the tip of the carrier gas introduction pipe is disposed obliquely downward by 20 to 50 ° with respect to the horizontal direction. An organometallic compound supply container.

  By using an organometallic compound supply container filled with a carrier-supporting organometallic compound coated with an organometallic compound that is solid at room temperature on a carrier inert to the organometallic compound of the present invention, a certain reproducible organometallic compound When the amount of vaporization of the organometallic compound is increased by increasing the flow rate of the carrier gas, the decrease in the usage rate of the filled organometallic compound can be reduced.

  The organometallic compound in the present invention is solid at room temperature and is used for vapor phase growth and the like, and specifically, trimethylindium, dimethylchloroindium, cyclopentadienylindium, trimethylindium / trimethyl Arsine adduct, indium compounds such as trimethylindium trimethylphosphine adduct, zinc compounds such as ethyl zinc iodide, ethylcyclopentadienyl zinc, cyclopentadienyl zinc, aluminum compounds such as methyldichloroaluminum, methyldichlorogallium, Examples thereof include gallium compounds such as dimethylchlorogallium and dimethylbromogallium, and biscyclopentadienylmagnesium.

Examples of the carrier inert to the organometallic compound that supports these organometallic compounds include ceramics such as alumina, silica, mullite, glassy carbon, graphite, potassium titanate, quartz, silicon nitride, boron nitride, and silicon carbide. Metals such as stainless steel, aluminum, nickel and tungsten, fluorine resin, glass and the like are used.
The shape of the carrier is not particularly limited, and various shapes such as an indefinite shape, a spherical shape, a fiber shape, a net shape, a coil shape, and a circular tube shape are used.
The carrier preferably has a large specific surface area, and preferably has a fine irregularity of about 100 to 2000 μm, or has a large number of pores (voids) in the carrier itself, rather than a smooth carrier surface. Examples of such carriers include alumina balls, Raschig rings, Helipac, Dickson packing, stainless sintered elements, glass wool, and the like.

  As a method of supporting the organometallic compound on the carrier, a method generally practiced in the past can be employed. For example, a method in which a carrier and an organometallic compound are put in a container in advance according to a weight ratio, and then this is heated to melt the organometallic compound, and then slowly cooled while rotating and stirring, while the organometallic compound is heated and melted Examples thereof include a method in which a carrier is charged and then an excess molten organometallic compound is extracted and then cooled.

  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 organometallic compound may be altered or contaminated, so that not only the quality of the resulting film is impaired when used for vapor phase growth, but also the present invention. This makes it impossible to stably supply the desired raw materials. In order to avoid such inconvenience, the carrier is preliminarily deaerated while being heated at a temperature within the allowable range of the material, and then the void is replaced with an inert gas such as nitrogen or argon. Things are recommended.

  The organometallic compound supported on the carrier is usually in the range of about 10 to 100 parts by weight, preferably about 20 to 70 parts by weight per 100 parts by weight of the carrier. If the amount is about 10 parts by weight or less, the amount of the organometallic compound occupying the container volume is small, so the container must be made larger than necessary, which is not economical. In addition, when the amount exceeds about 100 parts by weight, the surface area of the organometallic compound per filling volume does not increase as expected compared to the case where the amount is not supported. I can not get enough.

  FIG. 1 is a schematic cross-sectional view of one embodiment of the organometallic compound supply container of the present invention. The container 1 is usually a cylindrical one having a curved bottom. A carrier gas introduction pipe 2 and a carrier gas lead-out pipe 4 are attached to the upper part of the container 1, and the tip 3 of the carrier gas introduction pipe is obliquely downward with respect to the horizontal direction at about 20 to 50 °, preferably about 25 to 25 °. It is disposed with an inclination of 45 °. The tip 5 of the carrier gas outlet tube is disposed at the bottom of the container. The inside of the container is filled with an organometallic compound 6 supported on a carrier. FIG. 4 is a schematic cross-sectional view of a conventional organometallic compound supply container. The supply container of the present invention is different from the conventional supply container in which the tip 3 of the carrier gas introduction pipe is arranged vertically. The difference is that the tip 3 of the tube is disposed at an angle of about 20-50 °. The container 1 is provided with an inlet (not shown) for the organometallic compound and carrier or the carrier-supporting organometallic compound.

  The carrier gas introduction pipe 2 and the carrier gas lead-out pipe 4 are attached to the top of the container in FIG. 1, but the tip 3 of the carrier gas lead-in pipe is at the top of the container and the tip 5 of the carrier gas lead-out pipe is the container. As long as it is disposed at the bottom of the container, it may be the side of the container.

The tip 3 of the carrier gas introduction pipe is inclined about 20 to 50 ° obliquely downward with respect to the horizontal direction, and is inclined with respect to the side wall of the container from a position away from the central axis of the container. It is preferable.
FIG. 2 is a schematic cross-sectional view showing the arrangement in the planar direction of the tip of the carrier gas introduction tube. The carrier gas introduction pipe 2 is disposed at a position away from the central axis of the cylindrical container, and its tip 3 is disposed to be inclined with respect to the side wall of the container. With this arrangement, the carrier gas from the tip portion flows in a swirling flow (schematically indicated by arrows in the figure), and there is no drift.

  FIG. 3 is a diagram showing an example of the structure of the tip of the carrier gas introduction pipe. In (A), the opening part of the part of the top plate 7 of the container is inclined about 20 to 50 ° obliquely downward with respect to the horizontal direction to constitute the tip part. In (B), the top plate 7 is provided with a pipe inclined approximately 20 to 50 ° obliquely downward with respect to the horizontal direction to constitute the tip portion.

  The filling amount of the carrier-supported organometallic compound into the container is usually set at a lower portion than the tip of the carrier gas introduction tube. However, when the organometallic compound is supported on the carrier in the container, 30 to 70 of the container is used. It is about volume%.

Although a container having a curved bottom is shown, the present invention is not limited to this, and a conical container or the like can also be used. A container having a curved bottom is preferably used because it is easy to manufacture and can supply a constant concentration of gas stably and with high efficiency.
The distance between the bottom of the container and the tip 5 of the carrier gas outlet tube is about 2 to 15 mm, preferably about 2 to 10 mm, more preferably 2 to 5 mm. If it is larger than about 15 mm, the use rate of the organometallic compound decreases, which is not preferable.

  The supply container 1 filled with the organometallic compound supported on the carrier by the above-described method is transported to the place of use, the carrier gas outlet pipe 4 is connected to a vapor phase growth apparatus or the like (not shown), and the carrier The gas introduction pipe 2 is connected to a supply source of a carrier gas such as hydrogen gas. By holding the supply container at a constant temperature, supplying a carrier gas, and transferring the carrier gas from the upper part of the container to the lower part while removing the gap between the carrier-supported organometallic compounds, the organometallic compound having a constant concentration at the temperature is obtained. The containing carrier gas is supplied to the vapor phase growth apparatus or the like through the carrier gas outlet pipe 4. As a result, a certain reproducible amount of evaporation of the organometallic compound is obtained, and even when the amount of vaporization of the organometallic compound is increased by increasing the carrier gas flow rate, the decrease in the usage rate of the filled organometallic compound can be reduced. .

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these Examples.

The following containers were used as the organometallic compound supply containers.
(Container A)
A stainless steel container (curved bottom) having an internal volume of 800 ml, which is the same as schematically shown in FIGS. 1, 2 and 3A, and the carrier gas introduction pipe 2, A carrier gas outlet pipe 4, a carrier, and an inlet for an organometallic compound are provided. As shown in FIG. 3A, the tip of the carrier gas introduction pipe is configured such that the opening of the container top plate 7 is inclined 30 ° obliquely downward with respect to the horizontal direction. Further, as shown in FIG. 2, the carrier gas introduction pipe 2 is disposed at a position 24 mm away from the central axis of the cylindrical container, and the tip 3 thereof is disposed to be inclined with respect to the side wall of the container. Furthermore, the distance between the bottom of the container and the tip 5 of the carrier gas outlet tube is 3 mm.
(Container B)
A container similar to the container A, except that the tip of the carrier gas introduction pipe is oriented in a direction perpendicular to the container top plate as shown in FIG.

  The inside of the container and the conduit were purged with nitrogen, and then vacuum degassed as a carrier, and about 435 g of alumina balls having a diameter of about 4 mmφ and 300 g of trimethylindium were filled into the container from the inlet in a nitrogen atmosphere. The filled container was heated above the melting point of trimethylindium to melt the trimethylindium, and then gradually cooled while rotating the container to solidify and support the trimethylindium on the surface of the support alumina balls.

(Supplying organometallic compounds)
A hydrogen cylinder, a flow rate control device, an organometallic compound supply container filled with the above carrier-supporting organometallic compound, a gas concentration meter, a cryogenic trap for collecting trimethylindium, a pressure control device, and a vacuum pump were connected in this order.
The supply container was placed in a thermostatic bath and kept at 25 ° C. An epison densitometer (Thomas Swan Scientific Equipment Co., Ltd.) was used as the gas densitometer.

Experiment 1: For container A filled with a carrier-supported organometallic compound, hydrogen gas was supplied from a carrier gas introduction tube at 900 ml / min (at atmospheric pressure), trimethylindium was vaporized, and the trimethylindium concentration was measured with a gas densitometer. did.
Experiment 2: In addition, for the container B filled with the carrier-supporting organometallic compound, hydrogen gas was supplied from the carrier gas introduction tube at 900 ml / min (at atmospheric pressure), and the trimethylindium concentration was measured in the same manner.
Experiment 3: For the container B filled with the carrier-supporting organometallic compound, hydrogen gas was supplied from the carrier gas introduction tube at 600 ml / min (in terms of atmospheric pressure), and the trimethylindium concentration was measured in the same manner.
The ratio of these usage rates (ratio of the total weight of trimethylindium vaporized while a constant concentration of trimethylindium gas was obtained to the amount of trimethylindium charged in the container) (based on Experiment 1) was determined. The results are shown in Table 1.

  As described above, when the conventional container (B) is used, the usage rate decreases when the hydrogen gas flow rate is increased, but even if the hydrogen gas flow rate is increased by using the container (A) of the present invention, The usage rate can be increased as compared with the case where a conventional container is used.

It is a cross-sectional schematic diagram of one embodiment of the organometallic compound supply container of the present invention. It is a cross-sectional schematic diagram which shows arrangement | positioning of the plane direction of the front-end | tip part of a carrier gas introduction pipe. It is a figure which shows the example of the structure of the front-end | tip part of a carrier gas introduction pipe | tube. It is a cross-sectional schematic diagram of the conventional organometallic compound supply container.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Container 2 Carrier gas introduction pipe 3 Tip part of carrier gas introduction pipe 4 Carrier gas outlet pipe 5 Tip part of carrier gas outlet pipe 6 Carrier-supporting organometallic compound 7 Top plate of container

Claims (4)

  The tip of the carrier gas inlet tube is arranged at the top of the container, the tip of the carrier gas outlet pipe is arranged at the bottom, and the carrier inert to the organometallic compound is coated with a solid organometallic compound at room temperature. In the organometallic compound supply container filled with the carrier-supported organometallic compound, the tip of the carrier gas introduction pipe is disposed obliquely downward by 20 to 50 ° with respect to the horizontal direction. Organometallic compound supply container.   The container is cylindrical, and the tip of the carrier gas introduction pipe is inclined 20 to 50 ° obliquely downward with respect to the horizontal direction, and is inclined with respect to the side wall of the container from a position away from the central axis of the container. The organometallic compound supply container according to claim 1, wherein the organometallic compound supply container is arranged as follows.   3. The organometallic compound supply container according to claim 1, wherein a distance between the bottom of the container and the tip of the carrier gas outlet pipe is 2 to 15 mm. The organometallic compound supply container according to claim 1, wherein the organometallic compound is trimethylindium.

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