JP5521681B2 - Organometallic compound feeder - Google Patents

Description

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

  In the production of compound semiconductor devices, the MOCVD method (metal organic chemical vapor deposition method) is generally used. In the MOCVD method, it is important to stably supply a gasified organometallic compound at a constant concentration over a long period of time, and a supply device is used for this purpose.

  An example of this type of supply apparatus is disclosed in Patent Document 1. The supply device disclosed in Patent Document 1 includes a first container having a carrier gas introduction port provided at an upper portion, a second container having a carrier gas outlet port provided at an upper portion, and a first container, And a communication pipe that communicates the second container at its lower end.

  According to the supply device disclosed in Patent Document 1, since the carrier gas efficiently contacts the organometallic compound and the vaporized organometallic compound can be transported well by the carrier gas, the organometallic compound is stable over a long period of time. Can be supplied.

International Publication No. 07/139159

  In recent years, in order to be able to continuously manufacture a compound semiconductor device for a longer period of time, in a supply apparatus, it is required to be able to continuously supply an organometallic compound for a longer period of time. The simplest way to do this is to increase the capacity of the container.

  As a method for increasing the capacity of the container, it is conceivable to use a container having a higher height or a container having a larger diameter. However, in order to supply the organometallic compound at a constant concentration, it is necessary to keep the container at a constant temperature. Usually, the container is installed in a thermostatic bath, which limits the height of the container. Moreover, when the height of the container is high, it becomes difficult to fill the organometallic compound, and workability at the time of filling the organometallic compound is lowered. Therefore, it is not realistic to use a container having a high height, and it is a realistic method to use a container having a large diameter.

  However, when a container with a large diameter is used, the cross-sectional area of the container increases, making it difficult to make the carrier gas uniformly contact the organometallic compound over the entire cross section of the container. In other words, so-called channeling, in which a specific flow path is formed, is likely to occur. When channeling occurs, the proportion of the organometallic compound that comes into contact with the carrier gas decreases, so that more organometallic compound remains in the container without being carried by the carrier gas. As a result, the utilization efficiency of the organometallic compound is lowered, and there is a possibility that the effect obtained by increasing the capacity of the container cannot be obtained.

  In general, channeling in which a specific flow path is formed in a layer of an organometallic compound by introducing a carrier gas into a container is a ratio of an axial length L to a cross-sectional area S of the container, that is, L / S. The smaller the value, the more likely it is. Here, the cross-sectional area S and the length L are the inner dimensions of the container.

  An object of the present invention is to provide an organometallic compound supply apparatus that is less likely to cause channeling even when the capacity of a container is increased and can stably supply an organometallic compound for a longer period of time.

The organometallic compound supply device of the present invention is a supply device for supplying an organometallic compound that is solid at room temperature in association with a carrier gas,
A column-type first container provided with a carrier gas inlet at the top;
A column-type second container provided with an outlet for the carrier gas at the top;
A communication member that communicates the inside of the first container and the inside of the second container at its lower end;
Have
The inside of the first container is filled with the organometallic compound, and the flow direction of the carrier gas is vertical from the side where the gas introduction port is provided to the side where the communication member is communicated. Is divided into a plurality of spaces communicating in order ,
A wire mesh configured to support the organometallic compound is provided at the lower end of the space in which the carrier gas flows from top to bottom among the plurality of spaces, and the carrier is provided. A portion where the gas flow is reversed from upward to downward is not filled with the organometallic compound .

  In the supply device of the present invention, the first container has a plurality of cylindrical bodies arranged with the axial direction directed in the vertical direction, and a plurality of spaces are formed by the plurality of cylindrical bodies. Good. In this case, the plurality of cylindrical bodies are arranged concentrically, the gas introduction port is provided in the innermost cylindrical body, and the communication member is connected to the outermost cylindrical body. preferable.

  According to the present invention, an organometallic compound that is solid at room temperature can be stably supplied from a larger capacity container for a longer time.

It is typical sectional drawing of the supply apparatus of the organometallic compound by one Embodiment of this invention.

  Referring to FIG. 1, an apparatus for supplying an organometallic compound according to an embodiment of the present invention is shown. This supply apparatus has two column-type containers 10A and 10B arranged in parallel at a distance from each other, and a communication pipe 5 that communicates the inside of the two containers 10A and 10B at the lower ends of the containers 10A and 10B. doing.

  A gas introduction pipe 2 constituting a gas introduction port for introducing a carrier gas into the container 10A is attached to the upper end portion of one container 10A. A gas outlet pipe 3 that constitutes a gas outlet for leading the gas in the container 10B to the outside is attached to the upper end of the other container 10B. Each container 10A, 10B is filled with an organometallic compound 6 that is solid at room temperature. The capacity of the container 10A to which the gas introduction pipe 2 is attached is larger than the capacity of the container 10B to which the gas outlet pipe 3 is attached.

  As long as the shape of the containers 10A and 10B is a column type, for example, a cylindrical shape, a triangular cylindrical shape, a square cylindrical shape, a hexagonal cylindrical shape or the like can be used, and among these, the cylindrical container 10A 10B is preferably used. The shapes of the two containers 10A and 10B may be the same or different from each other.

  The total capacity of the two containers 10A and 10B is not particularly limited, but considering practicality, it is preferably in the range of 10 to 5000 ml, more preferably in the range of 10 to 3000 ml, particularly preferably 25 to 1600 ml. It is.

  The shape and structure of the communication pipe 5 are not particularly limited as long as they communicate with each other so that gas can flow between the two containers 10A and 10B. For example, by bending a single straight pipe, the two containers 10A, 10B are formed into a predetermined shape that can communicate at the lower end, a plurality of straight pipes connected to form a predetermined shape, and A U-shaped pipe or the like can be used as the communication pipe 5. From the viewpoint of designing the communication pipe 5, it is desirable that the communication pipe 5 is a straight pipe.

  The length of the communication pipe 5 is not particularly limited, and can be appropriately designed according to the size and arrangement of the two containers 10A and 10B. Further, the diameter of the communication pipe 5 is not particularly limited as long as the cross-sectional area of the communication pipe 5 is smaller than the cross-sectional area of the containers 10A and 10B at the connection portions with the containers 10A and 10B.

  As long as the gas introduction pipe 2 and the gas outlet pipe 3 are positioned at the upper ends of the containers 10A and 10B, respectively, the shape, size, and the attachment angle with respect to the containers 10A and 10B are not particularly limited.

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

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

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

  The organometallic compound 6 filled in the containers 10A and 10B is preferably a crushed carrier-supported organometallic compound obtained by crushing an organometallic compound that is solid at room temperature on the carrier as described above. It is a thing. Therefore, the crushed material includes both the organometallic compound that is supported on the carrier and the organometallic compound that has fallen off from the carrier due to the crushing. The crushed material has various sizes by crushing, and the particle size is not particularly limited. However, in order to ensure good contact with the carrier gas, the particle size is preferably 6.0 mm or less, and more preferably 4.76 mm or less.

  The carrier gas introduced into the container 10A from the gas introduction pipe 2 is not particularly limited as long as it is inert with respect to the organometallic compound 6 filled in the container 10A. For example, argon gas, nitrogen gas, Helium gas and hydrogen gas can be used. In addition, these carrier gas may be used independently and may be used in mixture of 2 or more types.

  Here, the internal structure of the container 10A to which the carrier gas introduction pipe 2 is attached will be described in detail. The container 10A is configured as described below in order to increase the capacity.

  The container 10A has three cylindrical bodies 11, 12, and 13 arranged concentrically with the axial direction as the vertical direction. The innermost cylindrical body 11 is connected to the gas introduction pipe 2 at the upper end and is closed except for the connecting portion, the lower end is positioned above the lower ends of the other cylindrical bodies 12 and 13, and the wire mesh 14 is By being attached, gas can be distributed. By attaching the metal mesh 14 to the lower end of the cylindrical body 11, most of the organometallic compound 6 filled in the cylindrical body 11 can be supported by the metal mesh 14.

  The intermediate cylindrical body 12 is open at the upper end but closed at the lower end. The outer cylindrical body 13 constitutes a part of the outline of the container 10A, and the upper end is closed, but a wire mesh 15 is attached to the lower end. The metal mesh 15 is attached so as to be in contact with the lower end of the intermediate cylindrical body 12.

The metal meshes 14 and 15 have a pore diameter, a pore density, and the like so that gas can be circulated but most of the organometallic compound 6 can be supported. A similar wire mesh 16 is also installed at the bottom of the other container 10B. As these wire meshes 14 to 16, a stainless steel wire mesh having a 40 mesh (hole diameter 0.4 mm, wire diameter 0.3 mm, hole density of about 200 holes / cm ² ) can be used.

  With the configuration of the container 10A as described above, the inside of the container 10A is formed inside the inner cylindrical body 11, and the first space S1 communicating with the gas introduction pipe 2 at the upper portion, the inner cylindrical body 11 and Formed between the intermediate cylindrical body 12, the second space S2 communicating with the first space S1 at the bottom, and formed between the intermediate cylindrical body 12 and the outer cylindrical body 13, The upper part is partitioned into three spaces, a third space S3 that communicates with the second space S2. As a result, inside the container 10A, the space S1 is formed in the upper and lower parts of the container so that the carrier gas flows in the vertical direction from the side where the gas introduction pipe 2 is connected to the side where the communication pipe 5 is connected. A gas path in which ~ S3 communicates in order is formed. Each space S1 to S3 is filled with an organometallic compound 6.

In order to be able to satisfactorily fill the organometallic compound 6 in all the spaces S1 to S3, in this embodiment, the three filling ports 4A configured to be openable and closable are respectively above the spaces S1 to S3. Located at the top of the container 10A. In particular, the filling port 4 </ b> A for filling the organometallic compound 6 in the space S <b> 1 is provided in an intermediate portion of the gas introduction pipe 2. With such a configuration, each of the spaces S1 to S3 can be individually filled with the organometallic compound 6 from each filling port 4A. In such an arrangement of the filling port 4A, the metal nets 14 and 15 are attached to the lower ends of the inner cylindrical body 11 and the outer cylindrical body 13, respectively, thereby filling the spaces S1 and S3 in the organic space. The amount of the metal compound 6 can be made constant.

  Similarly, with respect to the other container 10B, a filling port 4B is provided at an intermediate portion of the gas outlet pipe 3, from which the organometallic compound 6 can be filled into the container 10B.

  For filling the containers 10A and 10B with the organometallic compound 6, a known method generally used in this type of supply apparatus can be used. For example, the organometallic compound 6 can be filled into the containers 10A and 10B by introducing the solid organometallic compound 6 into the containers 10A and 10B from the respective filling ports 4 in an inert gas atmosphere.

  In the supply apparatus of this embodiment, the gas introduction pipe 2 is connected to a carrier gas source (not shown) in a state where the containers 10A and 10B are filled with the organometallic compound 6, and the gas outlet pipe 3 is connected to, for example, a vapor phase growth apparatus. Used in connection with (not shown).

  The carrier gas is introduced from the carrier gas source to the supply device while the supply device is maintained at a constant temperature. The introduced carrier gas is supplied to the vapor phase growth apparatus while being in contact with the organometallic compound 6 through a path of the gas introduction pipe 2 → the container 10A → the communication pipe 5 → the container 10B → the gas outlet pipe 3. The organometallic compound 6 vaporized in each of the containers 10A and 10B by contact with the carrier gas accompanies the flow of the carrier gas, whereby the vaporized organometallic compound 6 is supplied to the vapor phase growth apparatus together with the carrier gas. The

  In such a gas flow path, the communication pipe 5 connects the lower ends of the containers 10 </ b> A and 10 </ b> B, so that the carrier gas that has reached the lower end of the container 10 </ b> A with the organometallic compound 6 passes through the communication pipe 5. Is introduced into the inside of the container 10B from the lower end of the container 10B. Further, after coming into contact with the organometallic compound 6 filled in the container 10B, the inside of the container 10B is raised and led out from the gas outlet pipe 3. . By configuring the supply device so that the cariga gas flows through such a path, the carrier gas can be efficiently brought into contact with the organometallic compound 6, and the organometallic compound 6 can be stably supplied.

  Furthermore, in this embodiment, since the container 10A has the internal structure as described above, the carrier gas flows through the following path inside the container 10A.

  The carrier gas introduced from the gas introduction pipe 2 first flows from the upper part to the lower part of the first space S1. The carrier gas that has reached the lower portion of the first space S1 passes through the wire mesh 14, spreads outward, and flows into the second space S2. Since the lower end of the cylindrical body 12 is closed, the carrier gas that has entered the second space S2 flows from the lower part toward the upper part in the second space S2. When the carrier gas reaches the upper end of the second space S2, the carrier gas collides with the upper wall of the container 10A, spreads outside, and flows into the third space S3. Then, the carrier gas that has entered the third space S3 flows from the upper part toward the lower part in the third space S3, passes through the wire mesh 15, and travels toward the communication pipe 5.

  As described above, the inside of the container 10A is partitioned into the three spaces S1 to S3 by the cylindrical bodies 11 to 13 arranged with the axial direction directed in the vertical direction, and the carrier gas sequentially separates these spaces S1 to S3. Even when the cross-sectional area of the container 10A is increased in order to increase the capacity of the container 10A, the carrier gas introduced into the container 10A always passes through the layer of the organometallic compound 6. Moreover, the cross-sectional area of the space through which the carrier gas actually flows is smaller than the case where the interior of the container 10A is not partitioned into a plurality.

  Therefore, compared with the case where the container 10A is not divided into a plurality of spaces S1 to S3, the flow rate of the carrier gas in the container 10A is increased, and the occurrence of channeling can be suppressed.

  In the present embodiment, the carrier gas changes its flow direction when flowing into the second space S2 from the first space S1 and when flowing into the third space S3 from the second space S2. It flows so as to reciprocate up and down 10A. The change in the direction of the flow of the carrier gas occurs when the carrier gas collides with the inner wall of the container 10A. This collision has an effect of dispersing the carrier gas and has an effect of further suppressing the occurrence of channeling.

  Furthermore, in this embodiment, by arranging the three cylindrical bodies 11 to 13 concentrically, the carrier gas introduced into the central portion of the container 10A passes from the first space S1 through the second space S2. In the process of flowing into the third space S3, the container 10A is configured to spread outside the container 10A. This also brings about an effect of dispersing the carrier gas when the carrier gas flows into the second space S2 from the first space S1 and when flowing into the third space S3 from the second space S2, It is effective in suppressing channeling.

  In the present embodiment, the metal mesh 15 is attached so as to contact the lower end of the intermediate cylindrical body 12, and the organometallic compound 6 is substantially filled between the lower end of the cylindrical body 12 and the metal mesh 15. It is said that the structure is not. Even if there is a gap between the lower end of the cylindrical body 12 and the metal mesh 15, and even if the gap can be filled with the organometallic compound 6, the organometallic compound 6 present in the gap can hardly contact the carrier gas. By attaching the wire mesh 15 so as to contact the lower end of the cylindrical body 12 as described above, the organometallic compound 6 can be used more effectively.

The dimension of the cylindrical bodies 11-13 is not specifically limited. Below, the preferable dimension of the cylindrical bodies 11-13 is illustrated. The inner cylindrical body 11 preferably has an inner diameter of 18 to 46 mm, an outer diameter of 21 to 49 mm, a length (height) of 133 to 143 mm, and a cross-sectional area of 2.5 to 16.6 cm ² . The intermediate cylindrical body 12 preferably has an inner diameter of 57 to 85 mm, an outer diameter of 60 to 90 mm, a length (height) of 133 to 143 mm, and a cross-sectional area of 7.0 to 53.0 cm ² . The outer cylindrical body 13 preferably has an inner diameter of 97 to 135 mm, an outer diameter of 101 to 140 mm, a length (height) of 139 to 149 mm, and a cross-sectional area of 11.5 to 114.3 cm ² .

  On the other hand, for the container 10B provided with the gas outlet pipe 3, the carrier gas flows mainly in the axial direction of the container 10B inside the container 10B. Therefore, the inner dimension of the container 10B is such that the ratio of the height to the diameter is 0.8 to 10.0 so that the carrier gas flowing through the container 10B can efficiently contact the organometallic compound 6 in the container 10B. It is preferable that it is 1.2 to 10.0. This value assumes a case where the container 10B is cylindrical, but if it is not cylindrical, it may be considered as a circular diameter having an area equal to the cross-sectional area from the cross-sectional area.

  By setting the aspect ratio of the container 10B within the above range, channeling in the container 10B can be suppressed, and a more stable supply amount of the organometallic compound 6 can be maintained.

  As mentioned above, although preferable embodiment was described as an example about this invention, a various change is possible for this invention within the range of the technical idea of this invention.

  For example, in the embodiment shown in FIG. 1, the inside of the container 10A is divided into three spaces S1 to S3 by three cylindrical bodies 11 to 13, but the arrangement of the divided spaces is the carrier in each space. Any arrangement can be used as long as the gas flow direction is in the vertical direction and the gas flow direction is communicated in order from the side connected to the gas introduction pipe 2 to the side connected to the communication pipe 5. The number of can also be 4 or more. However, since the gas introduction pipe 2 is normally connected to the upper part of the container 10A and the communication pipe 5 is connected to the lower part of the container 10A, for example, the lower part of the upstream space and the downstream space in the gas flow direction. When the inside of the container 10A is partitioned into a plurality of spaces by partition walls (tubular bodies 11 and 12) as in the present embodiment rather than communicating with the upper part of the container using a pipe or the like (not shown) The number of spaces is an odd number of 3 or more.

  Further, in the above-described form, the filling port 4A for filling the space S1 of the container 10A with the organometallic compound 6 and the filling port 4B for filling the container 10B with the organometallic compound 6 are the gas introduction pipe 2 and the gas outlet, respectively. Although the example provided in the intermediate part of the pipe | tube 3 was shown, these filling ports 4A and 4B can also be provided separately from the gas inlet tube 2 and / or the gas outlet tube 3.

  Furthermore, in the above-described embodiment, the example in which the two containers 10A and 10B are arranged apart from each other is shown, but they may be arranged in contact with each other. Regarding the mutual positional relationship of the containers 10A and 10B, in the above-described embodiment, the example in which the two containers 10A and 10B are arranged in parallel has been shown. The mutual positional relationship is not particularly limited.

2 Gas introduction pipe 3 Gas outlet pipe 4 Filling port 5 Communication pipe 6 Organometallic compound 10A, 10B Container 11, 12, 13 Tubular body 14, 15, 16 Wire mesh

Claims (5)

A supply device for supplying an organometallic compound that is solid at room temperature with a carrier gas,
A column-type first container provided with a carrier gas inlet at the top;
A column-type second container provided with an outlet for the carrier gas at the top;
A communication member that communicates the inside of the first container and the inside of the second container at its lower end;
Have
The inside of the first container is filled with the organometallic compound, and the flow direction of the carrier gas is vertical from the side where the gas introduction port is provided to the side where the communication member is communicated. Is divided into a plurality of spaces communicating in order ,
A wire mesh configured to support the organometallic compound is provided at the lower end of the space in which the carrier gas flows from top to bottom among the plurality of spaces, and the carrier is provided. An organometallic compound supply apparatus, wherein a portion where the gas flow is reversed from upward to downward is not filled with the organometallic compound.   2. The supply according to claim 1, wherein the first container has a plurality of cylindrical bodies arranged with an axial direction directed in a vertical direction, and the plurality of spaces are formed by the plurality of cylindrical bodies. apparatus.   The plurality of cylindrical bodies are arranged concentrically, the gas introduction port is provided in the innermost cylindrical body, and the communication member is connected to the outermost cylindrical body. The supply device described. Among the plurality of spaces, the carrier gas flows from the top to the bottom in the space where the gas introduction port is provided and the space where the communication member communicates, and the carrier gas flows from the bottom to the top in the second container. The supply device according to any one of claims 1 to 3, wherein the supply device is configured to flow toward the front. The supply device according to any one of claims 1 to 4, wherein the number of the spaces defined in the first container is an odd number of 3 or more.

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