JP4571787B2 - Filling container for solid organometallic compound and filling method thereof - Google Patents

Description

  The present invention relates to a filled container of a solid organometallic compound and a filling method thereof. More specifically, a solid organometallic compound that is a material for vapor phase epitaxial growth by a Metalorganic Chemical Vapor Deposition (hereinafter abbreviated as “MOCVD”) method or the like used when manufacturing materials for electronic industry such as compound semiconductors, The present invention relates to a filling container that can be stably supplied to a vapor phase epitaxial growth apparatus at a constant concentration for a long period of time and a method of filling a solid organometallic compound.

  Organometallic compounds are widely used as raw materials for producing materials for the electronic industry.

  In recent years, vapor phase epitaxial growth by the MOCVD method or the like is frequently used as a method for producing materials for electronic industry using an organometallic compound. For example, a thin film of a compound semiconductor is manufactured by the MOCVD method, and an organic metal compound such as trimethylaluminum, trimethylgallium, or trimethylindium is used as a raw material.

  When these organometallic compounds are used in the MOCVD method, when the organometallic compound is solid, the carrier gas inlet (2a) and the carrier gas outlet as shown in FIG. (3a) is filled in a filling container A, a carrier gas such as hydrogen gas is introduced into the container from the carrier gas inlet (2a), and the organometallic compound is introduced into the carrier gas from the carrier gas outlet (3a). A method of taking out as a saturated gas and supplying it to the MOCVD apparatus is used.

  In this case, when the organometallic compound is solid at the temperature used in the above supply, the carrier gas passes through the solid organometallic compound in the filled container A without making sufficient contact with the solid organometallic compound. It is difficult to maintain a uniform contact state between the carrier gas and the solid organometallic compound due to the formation of a flow path, and the carrier gas is stably solid from the filling container A to the MOCVD apparatus at a constant concentration for a long period of time. There is a problem that it is difficult to supply the organometallic compound. In addition, in the supply of the solid organometallic compound by the method using the carrier gas as described above, if the amount of the solid organometallic compound filled in the filling container A is increased, it can be stably supplied to the MOCVD apparatus. The proportion of the amount of the solid organometallic compound is reduced with respect to the amount of the filled solid organometallic compound, and as a result, the remaining amount of the solid organometallic compound in the filling container increases and the solid organometallic compound cannot be used effectively. There is a problem.

  In order to solve these problems, various proposals have been made regarding methods for filling a solid container A with a solid organometallic compound. For example, Patent Literature 1, Patent Literature 2, Patent Literature 3, Patent Literature 4 and Patent Literature 5 propose a method of filling a solid container with a solid organometallic compound together with a filler. For example, Patent Document 6 proposes a method in which a solid organometallic compound is coated on an inert carrier and filled in a filling container A.

  In addition to the above, various proposals have been made for the structure of the filling container itself filled with the solid organometallic compound in the method for solving the above-mentioned problems. For example, in Patent Document 7 and the like, as shown in FIG. 16, a diffuser (20a) for making the gas uniform is provided at the carrier gas inlet, and the carrier gas is uniformly distributed to the solid organometallic compound. A filling container B has been proposed.

Further, for example, Patent Document 8 proposes a filling container C having a solid organometallic compound arrangement chamber (21a) having air permeability as shown in FIG.
Japanese Patent Publication No. 5-39915 Japanese Patent Publication No.6-20051 JP 7-58023 A JP-A-8-250440 JP-A-8-299778 Japanese Patent No. 2651530 Japanese Patent Publication No. 2-12496 JP-A-10-223540

  However, the conventional filling container A includes a carrier gas inlet (2a) and a carrier gas outlet (3a) in a single container as shown in FIG. The structure is provided with a dip tube having a lower opening (7a) as a flow path (8a) up to the bottom of the filling container A. As a result of investigation by the present inventor, when the filled container A having the structure of FIG. 15 is used, supply of the organometallic compound by the carrier gas in supplying the solid organometallic compound to the MOCVD apparatus in the method using the carrier gas. It has been clarified that there is a phenomenon that the supply amount of the organometallic compound in the carrier gas gradually decreases as the period becomes longer. In particular, when the filling amount of the solid organometallic compound is increased or the carrier gas flow rate is increased, the effect on the supply stability of the solid organometallic compound is remarkably reduced. Thus, in the filled container A, an effect sufficient for supplying the solid organometallic compound to the MOCVD apparatus stably for a long period of time is not obtained.

  Also, various proposed filling containers other than those shown in FIG. 15 are insufficient for supplying the solid organometallic compound to the MOCVD apparatus stably for a long time in the method using the carrier gas, or the appearance of the filling container There is a problem that the shape becomes remarkably large.

  Thus, the conventional filled container for a solid organometallic compound has various problems, and improvements are desired with respect to the supply stability of the solid organometallic compound and the appearance shape of the filled container not significantly increasing.

  The present invention solves the above-described problems, and a novel filling container capable of stably supplying a solid organometallic compound to a vapor phase epitaxial growth apparatus such as an MOCVD apparatus at a constant concentration for a long period of time and its filling The present invention relates to a method of filling a container with a solid organometallic compound.

  As a result of the study by the present inventors to solve the above-mentioned problems, the internal structure of the filling container is changed to a new structure having the following characteristics, and compared with a conventionally known filling container. The period during which solid organometallic compounds can be stably supplied at a constant concentration to a vapor phase epitaxial growth apparatus such as an MOCVD apparatus without significantly increasing the external shape, and the period during which the solid organometallic compounds are stably supplied The present invention has been completed.

  That is, the present invention relates to a solid organometallic compound filling container having a carrier gas introduction port and a carrier gas discharge port, wherein the inside of the filling container is divided into a plurality of vertical spaces, and the carrier gas introduced from the carrier gas introduction port is The present invention relates to a filled container for a solid organometallic compound characterized by having a structure that circulates through each vertical space and is discharged from a carrier gas discharge port.

  More specifically, the present invention relates to a filled container for a solid organometallic compound characterized by having the following requirements (a) to (c).

In filled containers for solid organometallic compounds,
(a) The inside of the filling container is vertically divided by at least one partition wall, and the inside of the filling container is divided into at least two spaces.
(b) The space inside the filling container formed by partitioning with a partition wall has a space having a carrier gas inlet and a space having a carrier gas outlet.
(c) The partition inside the filling container has a partition having an opening for flowing the carrier gas from the carrier gas inlet to the carrier gas outlet through each space in the filling container.

  Furthermore, the filling container for a solid organometallic compound of the present invention can have a filling port for filling the solid organometallic compound in a space inside the filling container formed by partitioning with a partition wall.

  In the filled container for a solid organometallic compound of the present invention, trimethylindium can be used as the solid organometallic compound.

  Furthermore, the present invention relates to a method for filling a solid organometallic compound, wherein the solid organometallic compound is filled into the filling container for a solid organometallic compound of the present invention.

  According to the present invention, in a filled container for a solid organometallic compound, a plurality of spaces are partitioned in a vertical direction by partition walls in the filled container, and each space has a structure in which a carrier gas flows, so that compared to a conventional filled container A solid organometallic compound can be stably supplied to a vapor phase epitaxial growth apparatus such as an MOCVD apparatus for a long period of time without increasing the external shape.

  The structure of the filling container of the present invention is not particularly limited as long as the internal space is divided into a plurality of vertical spaces and the carrier gas flows through each vertical space.

  Hereinafter, the filling container for solid organometallic compound and the filling method of the present invention will be described in more detail with reference to the drawings.

  An example of the filling container for solid organometallic compounds of this invention is shown in FIGS. As shown in FIGS. 1-4, the filling container for solid organometallic compounds of this invention partitions the inside of a filling container into the vertical direction by at least 1 or more partition (1), and is divided into at least 2 or more space. Has a structured. The partitioning method of the space by the partition wall (1) includes, for example, a structure in which the space is partitioned as shown in FIGS.

  The outer shape of the filling container can be, for example, a prismatic container such as a triangular prism, a quadrangular prism, a pentagonal prism, and a hexagonal prism in addition to a cylindrical container as shown in FIGS.

  Furthermore, the filling container for a solid organometallic compound of the present invention has a carrier gas inlet (2) leading to one space inside the filling container formed by partitioning with the partition wall (1), and one of the remaining spaces. A structure having a carrier gas discharge port (3) leading to, for example, the structure shown in FIGS. The carrier gas is introduced into the filled container filled with the solid organometallic compound from the carrier gas inlet (2), and the inside of the filled container is circulated, and the organometallic compound is saturated in the carrier gas from the carrier gas outlet (3). It is taken out as gas and supplied to the MOCVD apparatus. The installation positions of the carrier gas introduction port (2) and the carrier gas discharge port (3) in the filling container are, for example, the filling container according to the way of dividing the space by the partition wall (1), the form of use of the filling container, and the like. There is a structure having a carrier gas introduction port (2) and a carrier gas discharge port (3) in the upper part of the container, and a structure having them on the side surface of the filling container, for example.

  In the partition wall (1) inside the filling container of the present invention, as shown in FIGS. 1 to 4, the carrier gas is transferred from the carrier gas inlet (2) to the carrier gas outlet (3) through each space in the filling container. It has the partition (1) which comprises the opening part (4) for distribute | circulating, It is characterized by the above-mentioned.

  As an example of the partition wall (1) having the opening (4), for example, a structure having a structure shown in FIGS.

  The positions of these openings (4) are such that the carrier gas is sufficiently circulated from the carrier gas inlet (2) to the carrier gas outlet (3) through the space filled with the solid organometallic compound, and the solid filled at that time. There is no particular limitation as long as the organometallic compound is in sufficient contact with the carrier gas and does not interfere with the stable supply of the organometallic compound, but the filled solid organometallic compound and the carrier gas are not particularly limited. In order to make saturation contact effectively, in the opening (4) for flowing the carrier gas, when the opening (4) is arranged at the lower part of the partition wall (1), the inner height of the container from the inner bottom surface of the filling container. When the opening (4) is installed at a position of 1/3 or less, preferably 1/5 or less, more preferably 1/10 or less, and the opening (4) is arranged above the partition wall (1) Or inside bottom of filling container Container inner height of more than 2/3, preferably 4/5 or more, more preferably installing opening (4) to 9/10 or more positions.

  In the filling container of the present invention, the carrier gas flows through each partitioned space and is discharged from the carrier gas discharge port (3) by the above structure.

  In the filling container of the present invention, as an example of the partition wall (1) having the opening (4), as an example in the case of one partition wall (1), for example, a structure as shown in FIG. In addition, as an example in the case where there are two partition walls (1), for example, a structure as shown in FIG. 2 is shown. Further, as an example in the case where there are three or more partition walls (1), For example, the structure shown in FIG. 3 or 4 can be shown.

  Further, depending on the position of the opening (4) provided in the partition wall (1), the carrier gas is circulated through the space from the carrier gas inlet (2) through the opening (4) to the carrier gas outlet (3). In order to make it circulate, it can be set as the structure which provided the flow path (5) in each of the carrier gas introduction port (2) and the carrier gas discharge port (3). As an example of a filling container having a structure in which a flow path (5) is provided in each of the carrier gas introduction port (2) and the carrier gas discharge port (3), for example, one having a structure as shown in FIGS. I can do it.

  The flow path (5) is, for example, a tubular shape as shown in FIG. 9 or a flow path lower opening (6) at the lower part of the structure partitioned by the partition wall (1) as shown in FIG. 10 or FIG. It is possible to use those having The flow path (5) may be a combination of those having a tubular structure or a structure having a flow path lower opening (6) in the lower part of the structure partitioned by the partition wall (1).

  The position of the flow path lower opening (6) of this flow path (5) is 1/3 or less, preferably 1/5 or less, more preferably 1/10 or less of the container internal height from the inner bottom surface of the filling container. It is desirable to install in the position.

  The carrier gas distribution mode in the filling container of the present invention will be described with reference to FIG. First, the carrier gas is introduced from the carrier gas inlet (2) and circulates in the space having the carrier gas inlet (2). The carrier gas flows through each space through the opening (4), is discharged from the carrier gas discharge port (3), and is supplied to the MOCVD apparatus. In addition, although the distribution | circulation form of carrier gas was demonstrated based on FIG. 1, when the inside of a filling container was divided into three or more space like FIGS. 2-4, it was provided in each partition (1). The carrier gas flows through the opening (4).

  In this distribution form, in the structure in which the flow path (5) is provided in each of the carrier gas inlet (2) and the carrier gas outlet (3) as shown in FIG. 7, the carrier gas is the carrier gas inlet (2 ) And circulates in the space having the carrier gas inlet (2) after flowing through the flow path (5). The carrier gas flows through each space through the opening (4), flows through the flow path (5) provided in the carrier gas discharge port (3), is discharged from the carrier gas discharge port (3), and is supplied to the MOCVD apparatus. The

  When the solid organometallic compound is filled in the filling container of the present invention and used for supplying the organometallic compound to the MOCVD apparatus, the space inside the filling container is filled with the solid organometallic compound.

  In the filled container for the solid organometallic compound of the present invention, as a method for filling the filled container with the solid organometallic compound, a conventionally known method can be used as it is, for example, a solid organometallic compound. For example, a method for introducing and filling an organometallic compound into a filling vessel as saturated vapor in a carrier gas, and for example, a method for introducing an organometallic compound to a melting point or higher. A method of heating to a liquefied state and introducing into a filled container can be used.

  Furthermore, in the filling container for solid organometallic compounds of the present invention, a filling port (9) for filling the solid organometallic compound in the space inside the filling container formed by partitioning with the partition wall (1) may be provided. it can. By providing this filling port (9), the solid organometallic compound can be charged as it is. In this invention, the filling port of a filling container can be provided in the upper part of a filling container, for example like FIGS. Further, the carrier gas introduction port (2) and / or the carrier gas discharge port (3) can be separated from the filling container, so that the carrier gas introduction port (2) and / or the carrier gas discharge port (3) can be separated. And a filling port (9). The separated carrier gas introduction port (2) and / or carrier gas discharge port (3) and the filling container are used together again through the connecting part (26). As an example of this structure, for example, as shown in FIG. 12, a connecting part (26) that can be separated as a filling port is provided between the carrier gas introduction port (2) and the filling container, and the connection parts are joined together via this. What is used.

  The filling port may or may not be provided in the filling container depending on the filling method of the solid organometallic compound.

  In the filled container of the present invention, for example, as shown in FIGS. 1 to 4, the carrier gas inlet (2) and the carrier gas outlet (3) can be provided with a valve (22) that can be opened and closed, When the carrier gas is circulated, it is used with the valve (22) opened. When the organometallic compound is not supplied, the solid organometallic compound is usually contaminated from the outside with the valve closed, or sublimated outside the filling container. To prevent transpiration.

  Thus, the filling container of the present invention is divided into a plurality of spaces inside the filling container by the partition wall (1), and the carrier gas introduced from the carrier gas inlet (2) is a solid organic filled in each container space. In all the spaces in the metal compound, the structure passes from the upper part of the space to the lower part of the space and flows to the carrier gas discharge port (3). As described above, since the inside of the container is partitioned by the partition wall (1) and divided into a plurality of spaces, the cross-sectional area of each space is reduced and the contact between the carrier gas and the solid organometallic compound is sufficiently performed. The contact state between the carrier gas and the solid organometallic compound can be kept uniform without the formation of a flow path, and the solid organometallic compound can be stably transferred from the filling container to the MOCVD apparatus at a constant concentration for a long time by the carrier gas. It becomes possible to supply.

  Regarding the solid organometallic compound that can be used by filling the filling container of the present invention, not only the solid organometallic compound used in the filling container known so far, but also other solid organometallic compounds may be used. It is possible to apply a carrier gas having a saturated vapor pressure sufficient for a desired supply and a solid under supply conditions at a use temperature and pressure using the carrier gas. Representative examples of these solid organometallic compounds include alkyl metal compounds, metallocene compounds, β-diketone complexes, and adduct compounds. Specifically, for example, trimethylindium, dimethylchloroindium, triphenylaluminum, triphenylbismuth, alkyl metal compounds such as tert-butyllithium, metallocene compounds such as cyclopentadienylindium, biscyclopentadienylmagnesium, biscyclopentadienylmanganese, ferrocene, barium acetylacetonate complex, strontium acetylacetonate complex, copper acetyl Acetonate complex, calcium acetylacetonate complex, barium dipivaloylmethanate complex, strontium dipivaloylmethanate complex, copper dipivaloylmethanate complex, Β-diketone complexes such as thorium dipivaloylmethanate complex, calcium dipivaloylmethanate complex, trimethylindium trimethylarsine adduct, trimethylindium trimethylphosphine adduct, barium dipivaloylmethanate 1,10 -Adduct compounds, such as a phenanthroline adduct, etc. are mentioned.

  Moreover, the pressure when using the filling container of the present invention can be used without changing the conditions used in the filling containers known so far, and the solid organometallic compound can be stably MOCVD for a long period of time. The conditions are not particularly limited as long as the conditions are supplied to the apparatus, and any of pressurization, normal pressure, and reduced pressure can be used.

Further, the temperature at which the filling container of the present invention is used can be applied without changing the conditions used in the filling containers known so far, and the normally used solid organometallic compound is a carrier gas. On the other hand, it is possible to apply a condition in which a saturated vapor pressure sufficient for a desired supply is obtained and a solid is obtained under the supply conditions.
In the filling container of the present invention, any carrier gas used in known filling containers can be used. For example, inert gas such as nitrogen, argon, helium, or hydrogen gas is used. .

  Moreover, in the filling container of the present invention, a known filler that is used by being filled with a solid organometallic compound in a known filling container can be used. As the filler, for example, stainless steel, glass, ceramics, fluororesin or the like is used, and stainless steel can be preferably used. In addition, as the shape of the filler, various shapes such as a round shape, a square shape, a cylindrical shape, a coil shape, a spring shape, and a spherical shape can be used. For example, various packings for distillation such as Dixon packing, Helipak, Fenceke etc. can be used. A fibrous filler can also be used.

  These fillers can be used in the filling container of the present invention together with the solid organometallic compound after filling the filling container by a known method.

  In addition, the filling container of the present invention can be used not only for a solid organometallic compound but also for a filling container of a general solid substance such as a solid inorganic compound having a vapor pressure, a solid organic compound, or a solid metal. Thus, the filling container of the present invention can also be used as a filling container for taking out another solid substance as a gas saturated with the carrier gas instead of the solid organometallic compound.

  Hereinafter, the present invention will be described in detail by way of examples.

  The supply stability of the solid organometallic compound was tested using trimethylindium as the solid organometallic compound in the filled container shown in FIG.

  The supply stability test was conducted by the following method.

  In a nitrogen atmosphere, 400 g of trimethylindium and 647 g of a stainless steel filler were filled into a SUS filled container having an outer diameter of 76.0 mmφ as shown in FIG. 7 from the filling port (9).

  Next, the carrier gas outlet (3) was connected to a trap cooled with dry ice-methanol for collecting trimethylindium. The pipe connecting the carrier gas discharge port (3) and the trap cooled with dry ice-methanol was heated so that trimethylindium did not precipitate in the pipe. A filling container containing trimethylindium and a filler is attached to a thermostatic bath at 25 ° C., and nitrogen is supplied from the carrier gas inlet (2) of the filling container under the condition that the pressure in the apparatus system of the supply stability test is close to atmospheric pressure. The gas was flowed at 500 cc per minute, and the weight of trimethylindium collected in a trap cooled with dry ice-methanol every 8 hours was measured. In addition, the gas phase gas concentration of the carrier gas containing trimethylindium vapor was measured with an ultrasonic gas concentration meter (trade name Epison: manufactured by Thomas Swan).

  The result is shown in FIG. The vertical axis of the graph shown in FIG. 13 shows the supply amount of trimethylindium per hour, and the horizontal axis shows the usage ratio of the supplied trimethylindium in weight%.

  As a result of the supply stability test, when the filled container of the present invention was used, the supply rate of trimethylindium was stable up to 62% by weight of the usage ratio.

  In this way, by using the filling container of FIG. 7, the solid organometallic compound can be stably supplied at a constant concentration, and further, the solid organometallic compound can be obtained under the conditions where a stable supply rate is obtained. It becomes possible to increase the usage rate of. As a result, the period during which the solid organometallic compound is stably supplied can be improved by using the filled container of the present invention.

Comparative Example 1

  15 was filled with trimethylindium as a solid organometallic compound, and the supply stability of the solid organometallic compound was tested in the same manner as in Example 1. The result is shown in FIG. As a result of the supply stability test, when the conventional filled container A of FIG. 15 was used, the supply rate of trimethylindium was stable up to 35% by weight of the use ratio.

  The present invention can stably supply a solid organometallic compound to an apparatus for vapor phase epitaxial growth such as an MOCVD apparatus for a long period of time without increasing its external shape as compared with a conventional filled container.

(A) is a schematic cross-sectional view showing an embodiment of the filling container of the present invention, (B) is a plan view thereof, and (C) is a perspective view thereof. (A) is a schematic cross-sectional view showing an embodiment of the filled container of the present invention, (B) is a plan view thereof (A) is a schematic cross-sectional view showing an embodiment of the filled container of the present invention, (B) is a plan view thereof (A) is a schematic cross-sectional view showing an embodiment of the filled container of the present invention, (B) is a plan view thereof The perspective view which shows one Embodiment of the partition and opening part in the filling container of this invention The perspective view which shows one Embodiment of the partition and opening part in the filling container of this invention (A) is a schematic cross-sectional view showing an embodiment of the filling container of the present invention, (B) is a plan view thereof, and (C) is a perspective view thereof. (A) is a schematic cross-sectional view showing an embodiment of the filling container of the present invention, (B) is a plan view thereof, and (C) is a perspective view thereof. (A) is a perspective view which shows one Embodiment of the flow path of this invention, (B) is the sectional drawing. (A) is a perspective view showing an embodiment of a communication flow channel having a structure in which a partition wall in the filling container of the present invention also serves as a flow channel, and (B) is a sectional view thereof. (A) is a perspective view showing an embodiment of a communication channel having a structure in which a partition wall in the filling container of the present invention also serves as a channel, and (B) is a sectional view thereof. (A) is a schematic cross-sectional view showing an embodiment of a filling container having a connecting part with a structure in which the carrier gas introduction port and the filling port are combined in the filling container of the present invention, (B) is a plan view thereof, (C) is a plan view thereof. Perspective view The figure which shows the result of the test of the supply stability of the trimethylindium in this Example 1 (relationship between the usage rate of the supplied trimethylindium and the supply amount of trimethylindium per hour). The figure which shows the result (the relationship between the usage-amount of the supplied trimethylindium and the supply amount of the trimethylindium per hour) of the supply stability test of the trimethylindium in the comparative example 1. Schematic sectional view showing a conventional filling container A Schematic sectional view showing a conventional filling container B Schematic sectional view showing a conventional filling container C

Explanation of symbols

1: partition wall 2: carrier gas introduction port 3: carrier gas discharge port 4: opening 5: flow channel 6: flow channel lower opening 9: filling port 22: valve 26: connecting part 2a: carrier gas introduction port 3a: carrier Gas outlet 7a: Lower opening 8a: Channel 9a: Filling port 20a: Diffuser 21a: Solid organometallic compound placement chamber 22a: Valve 23a: Column type container 24a: Filter

Claims (5)

In a filled container for a solid organometallic compound having a carrier gas inlet and a carrier gas outlet,
(a) The inside of the filling container is partitioned vertically by at least one partition, and the inside of the filling container is partitioned into a space filled with at least two solid organometallic compounds.
(b) The space inside the filling container formed by partitioning with a partition wall has a space having a carrier gas inlet and a space having a carrier gas outlet.
(c) A solid organic metal having a partition wall having an opening for flowing the carrier gas from the carrier gas inlet to the carrier gas outlet through each space in the filler container in the partition wall inside the container Compound container (excluding those with a mesh structure in the space filled with the solid organometallic compound inside the container) . In the opening, when the opening is arranged at the lower part of the partition wall, it is 1/3 or less of the container inner height from the inner bottom surface of the filling container, and when the opening is arranged at the upper part of the partition wall, the inner bottom surface of the filling container 2. The filled container for a solid organometallic compound according to claim 1, wherein the opening is provided at a position of 2/3 or more of the inner height of the container. The filling container for a solid organometallic compound according to claim 1 or 2, further comprising a filling port for filling the space inside the filling container formed by partitioning with the solid organometallic compound. The filled container for a solid organometallic compound according to any one of claims 1 to 3, wherein the solid organometallic compound is trimethylindium. A solid organometallic compound filling method, comprising filling the solid organometallic compound filling container according to any one of claims 1 to 4 with a solid organometallic compound.

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