JP5521680B2 - 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 to stably supply the organometallic compound.

  As an example of a conventional supply apparatus, there is a supply apparatus disclosed in Patent Document 1. The supply apparatus disclosed in Patent Document 1 includes a container having a carrier gas introduction port and a discharge port, and an organometallic compound that is filled in the container and is solid at room temperature. The organometallic compound is a crushed product of the carrier-supported organometallic compound obtained by being crushed after being supported on an inert carrier, and further, a powder having a particle size of less than 0.84 mm by sieving Is not included.

  According to the supply device described in Patent Document 1, the organometallic compound is lengthened by limiting the minimum value of the particle size of the crushed material obtained by crushing the organometallic compound supported on the carrier as described above. It can be supplied stably over time. Specifically, in Patent Document 1, as a result of performing a supply stability test using Helipac and trimethylindium as a carrier and an organometallic compound, respectively, when the minimum particle size of the crushed material was not limited, Whereas the organometallic compound could only be stably supplied up to a usage rate of 45%, when the particle size of the crushed material was limited as described above, the organometallic compound was stably supplied up to a usage rate of 75%. It is described that it can be supplied.

  However, in the above-described conventional supply device, when the particle size is adjusted by sieving the crushed material, the organometallic compound eliminated by sieving is wasted, while the sieving is not performed The ratio of organometallic compounds that are not transported by the carrier gas and remain in the container is large. In either case, there is still room for improvement in the overall utilization efficiency of the organometallic compounds.

JP 2007-277703 A

  The objective of this invention is providing the supply apparatus of the organometallic compound which improves the comprehensive utilization efficiency of an organometallic compound.

  As a result of intensive studies by the present inventors in order to achieve the above object, a carrier-supporting organometallic compound is obtained by using a spherical carrier as the organometallic compound carrier and filling a container with a dispersing material for dispersing the carrier gas. It has been found that there is a case where the organometallic compound can be stably supplied up to a high use ratio without limiting the minimum particle size of the crushed material.

The supply device of the present invention is a supply device that supplies an organic metal compound that is solid at room temperature along with a carrier gas,
Container means having a carrier gas inlet and outlet;
An organometallic compound filled in the container means;
In the container means, a dispersion material filled in the upstream side of the organometallic compound in the flow direction of the carrier gas and dispersing the carrier gas introduced from the inlet,
Have
The organometallic compound is crushed after being supported on a spherical carrier, and is filled in the container means as a crushed material obtained without sieving those having a particle size of less than 0.84 mm. .

In the supply device of the present invention, the container means is
A column-type first container provided with an inlet at the top and filled with crushed material;
A column-type second container provided with an outlet at the top and filled with crushed material;
A communication member that communicates the inside of the first container and the inside of the second container at its lower end;
You may have.

  In this case, it is preferable that the dispersion material is filled in the first container. Furthermore, it is preferable that the dispersion material is packed in layers on the crushed material so as to cover the crushed material.

  According to the present invention, an organic metal compound that is solid at room temperature can be improved from the production of crushed materials to the supply of the organometallic compound during operation of the supply device, thereby improving the overall utilization efficiency of the organometallic compound. An organometallic compound supply apparatus suitable for the above can be provided.

It is typical sectional drawing of the supply apparatus of the organometallic compound by one Embodiment of this invention. It is typical sectional drawing of the supply apparatus of the organometallic compound which made the size of each container the same in FIG. FIG. 2 is a schematic cross-sectional view of an organometallic compound supply apparatus in which a filling port in FIG. 1 is separated from a gas introduction pipe. It is typical sectional drawing of the supply apparatus of the organometallic compound which has a single container. It is typical sectional drawing of the other example of the supply apparatus of the organometallic compound which has a single container. It is the graph of the relationship between the usage-amount of trimethylindium obtained by the stable supply test of Example 2, and the supply amount.

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

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

  Each container 1a, 1b is filled with a crushed material 10 of a carrier-supported organometallic compound obtained by pulverizing after supporting a solid organometallic compound on a carrier at room temperature. Furthermore, the dispersion material 11 for dispersing the carrier gas introduced from the gas introduction pipe 2 in the container 1 a is filled on the crushed material 10 in the container 1 a on the side where the gas introduction pipe 2 is attached. Has been. That is, the container 1a is filled with the crushed material 10 and the dispersion material 11 in this order from the bottom of the container 1a, and the dispersion material 11 is upstream of the crushed material 10 in the flow direction of the carrier gas inside the container 1a. Is filled. The dispersion material 11 is an aggregate of many members, and is filled in the container 1a with a gap between the members.

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

  For filling the crushed material 10 and the dispersion material 11 into the container 1a, a publicly known method can be used. For example, the crushed material 10 and the dispersion material 11 can be filled in the container 1a by introducing the crushed material 10 and the dispersion material 11 into the container 1a in this order from the filling port in an inert gas atmosphere. it can. The filling of the crushed material 10 into the container 1b can be performed in the same manner.

  The carrier gas introduced into the container 1a from the gas introduction pipe 2 is not particularly limited as long as it is inert with respect to the crushed material 10 and the dispersion material 11 filled in the containers 1a and 1b. Gas, nitrogen gas, helium gas, 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.

  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 crushed material 10 is formed by being crushed after being supported on a carrier inert to the organometallic compound. Therefore, the crushed material 10 filled in the containers 1a and 1b contains both the organometallic compound that is supported on the carrier and the organometallic compound that has fallen from the carrier due to the crushing. In the present invention, these are not individually distinguished, and include not only the organometallic compound actually supported on the carrier, but also the organometallic compound that has fallen off from the carrier and is not actually supported on the carrier. It is called thing 10.

  The crushed material 10 is made into 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. In particular, in the present invention, the crushed material 10 filled in the containers 1a and 1b includes the crushed material 10 having a particle size of less than 0.84 mm. The ratio of the crushed material 10 having a particle size of less than 0.84 mm is not particularly limited, but is preferably 1 g or less, more preferably 0.5 g or less, with respect to 1 g of the particle size of 0.84 mm or more.

  As a general carrier for supporting an organometallic compound, alumina sphere, helipac, sponge titanium, Dixon packing, and the like are known. In the present invention, at least a spherical carrier is used. Examples of the spherical carrier include zirconia sphere, alumina sphere, Teflon (registered trademark) sphere, stainless sphere, glass sphere, iron sphere, silicon nitride sphere, silicon carbide sphere, brass sphere, aluminum sphere, titanium sphere and the like. In addition, when using the support | carrier made from an alumina, there exist alpha-alumina and (gamma) -alumina in the kind of alumina, However, In this invention, alpha-alumina can be used preferably. The diameter of the spherical carrier is not particularly limited, but is preferably 0.1 mm to 4.0 mm, more preferably 0.3 mm to 2.0 mm. The spherical carrier may be mixed with a non-spherical carrier. The volume ratio of the spherical carrier to the non-spherical carrier is not particularly limited, but is preferably 1 or more. In addition, the spherical carrier may be a uniform size or two or more sizes. The ratio of the amount of the organometallic compound to 1 ml of the carrier in the crushed material 10 is not particularly limited, but is preferably 0.8 to 2.5 g, more preferably 0.9 to 2.0 g.

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

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

  The supply device of the present embodiment uses the gas introduction pipe 2 as a carrier gas source in a state where the container 1a is filled with the crushed material 10 and the dispersion material 11 and the container 1b is filled with the crushed material 10 as described above. In addition to being connected, the gas outlet pipe 3 is used by being connected to, for example, a vapor phase growth apparatus.

  Carrier gas is introduced into the supply device from the carrier gas source while the supply device is maintained at a constant temperature. The introduced carrier gas is supplied to the vapor phase growth apparatus through a path of the gas introduction pipe 2 → the container 1a → the communication pipe 5 → the container 1b → the gas outlet pipe 3.

  In the course of the carrier gas flow in the supply device, the carrier gas introduced into the container 1 a first comes into contact with the dispersion material 11. Since the dispersion material 11 is an aggregate of many members as described above and has gaps between the members, the carrier gas in contact with the dispersion material 11 is formed by the gaps between the members. It flows toward the bottom of the container 1a through a large number of flow paths, and contacts the crushed material 10 in a wide range. Since the carrier gas flows through the dispersion material 11 in this way, the carrier gas flow is dispersed by the dispersion material 11, so that the carrier gas is uniformly contacted with the crushed material 10 over almost the entire cross section of the container 1a. be able to. Therefore, the carrier gas efficiently contacts the crushed material 10, and the vaporized organometallic compound can be satisfactorily carried by the carrier gas.

  In order to more effectively exhibit the dispersion of the carrier gas by the dispersion material 11, the dispersion material 11 is formed in the container 1 a so as to cover the crushed material 10 from above and form a layer as shown in FIG. 1. Is preferably filled.

  The carrier gas that has passed through the layer of the dispersion material 11 passes through the layer of the crushed material 10 and reaches the bottom of the container 1a, and then is introduced into the container 1b through the communication pipe, while rising in the container 1b, It passes through the layer of crushed material 10 filled in 1b. When the carrier gas comes into contact with the organometallic compound in the crushed material 10 in the flow of the carrier gas, the organometallic compound is carried away by the carrier gas and consumed. The organometallic compound carried away by the carrier gas is led out from the gas outlet pipe 3 of the container 1b together with the carrier gas, and is supplied to the vapor phase growth apparatus.

  Conventionally, when a powder having a particle size of less than 0.84 mm is present in the crushed material 10, the pressure loss against the flow of the carrier gas is increased, so that a specific flow path is formed in the layer of the crushed material 10. As a result, carrier gas drift was likely to occur. However, as in the present invention, a spherical carrier is used as the carrier, and a powder having a particle size of less than 0.84 mm is present by filling the container with a dispersing material that disperses the carrier gas introduced into the container. Even if it does, a specific flow path is hard to be formed in the layer of the crushed object 10, and the contact efficiency of the crushed object 10 and carrier gas can be improved. As a result, the organometallic compound filled in the containers 1a and 1b can be stably supplied to the vapor phase growth apparatus up to a high usage rate equal to or higher than that when the particle size of the crushed material 10 is limited. .

  The reason for this is not clear, but when the consumption process (not shown) of the crushed material 10 was observed using a glass container, the spherical carrier moved relatively freely in the layer of the crushed material 10. For this reason, it is considered that the carrier moves to the gap between the crushed materials 10 formed according to the consumption of the organometallic compound, and the formation of the specific flow path is suppressed. On the other hand, when only a non-spherical carrier such as titanium sponge is used, the carrier is less likely to move compared to the spherical carrier, a specific flow path is formed in the layer of the crushed material 10, and the carrier gas drifts. It had occurred.

  Furthermore, in this embodiment, since the crushed material 10 having a particle size of less than 0.84 mm is not sieved, almost all of the organometallic compound used to obtain the crushed material 10 can be used, and the waste of the organometallic compound is Almost no.

  As described above, according to the present embodiment, the organometallic compound can be effectively used when the crushed material 10 is manufactured, and further, the crushed material filled in the containers 1a and 1b during operation of the supply device. Compared with the case where the particle size of 10 is limited, the organometallic compound can be stably supplied up to a use ratio equal to or higher than that. Therefore, it is possible to improve the overall utilization efficiency of the organometallic compound from the production of the crushed material 10 to the supply of the organometallic compound during operation of the supply device.

  As mentioned above, although this invention was demonstrated by showing typical embodiment, this invention is not limited to embodiment mentioned above, A various change is added within the range of the technical idea of this invention. it can.

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

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

  The carrier gas circulates inside the containers 1a and 1b mainly in the axial direction of the containers 1a and 1b. Therefore, the inner dimensions of the containers 1a and 1b are such that the ratio of the height to the diameter is 0.8 so that the carrier gas flowing in the containers 1a and 1b can be efficiently contacted with the organometallic compound in the containers 1a and 1b. It is preferable that it is-10.0, More preferably, it is 1.2-10.0. This value assumes the case where the containers 1a and 1b are cylindrical, but when the container is not cylindrical, it may be considered as a circular diameter having an area equal to the cross-sectional area from the cross-sectional area.

  By setting the aspect ratio of the containers 1a and 1b within the above range, it is possible to further suppress the formation of a gas flow path through which the carrier gas passes without being in efficient contact with the organometallic compound. The feed rate of the compound can be maintained.

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

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

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

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

  Further, in the above-described embodiment, the example in which the two containers 1a and 1b are arranged apart from each other is shown, but they may be arranged in contact with each other. Regarding the mutual positional relationship between the containers 1a and 1b, in the above-described embodiment, the example in which the two containers 1a and 1b are arranged in parallel is shown, but the lower ends of the two containers 1a and 1b are connected to each other. The mutual positional relationship is not particularly limited.

  The container means filled with the crushed material 10 has a structure in which the two containers 1a and 1b are connected to each other at the lower end in the above-described embodiment. However, the structure of the container means may be any structure generally used for this type of supply device as shown in FIGS.

  The supply device shown in FIG. 4 has a single container 101 filled with crushed material 110. A gas introduction pipe 102 constituting a gas introduction port for introducing a carrier gas into the container 101 is attached to the upper end of the container 101, while the gas in the container 101 is attached to the lower end of the container 101. A gas outlet pipe 103 that constitutes a gas outlet for leading the gas to the outside is attached. The container 101 is filled with a crushed material 110 obtained by carrying an organic metal compound that is solid at room temperature on a carrier and then crushed, and further, a carrier gas introduced from a gas introduction pipe 102 thereon. Is dispersed in layers in a container 101. A filling port 104 for filling the crushed material 110 and the dispersion material 111 into the container 101 is provided in an intermediate portion of the gas introduction pipe 102. Even when the supply apparatus shown in FIG. 4 is used, the crushed material containing particles having a particle size of less than 0.84 mm obtained by crushing after being supported on a spherical carrier as the crushed material of the carrier-supported organometallic compound. By using the same effect as described above can be obtained.

  The supply apparatus shown in FIG. 5 also has a single container 101 filled with crushed material 110 and having a lower diameter smaller than the upper part, and a carrier gas is introduced into the container 101 at the upper end thereof. For this purpose, a gas inlet tube 102 for extracting the carrier gas, a gas outlet tube 103 for extracting the carrier gas, and a filling port 104 for filling the crushed material 110 into the container 101 are attached. However, the gas outlet pipe 103 extends to the bottom of the container 101 inside the container 101, and a sintered metal filter is attached as a disperser 105 to the lower end thereof. The disperser 105 may not be attached. According to the supply device shown in FIG. 5, the carrier gas is supplied to the inside of the container 101 through the gas introduction pipe 102 and flows from the top to the bottom inside the container 101, while the dispersion material 111 and the crushing material are interposed therebetween. The object 110 is sequentially contacted. The carrier gas that has reached the lower portion of the container 101 flows into the gas outlet pipe 103 and is discharged to the outside of the container 101 through the gas inlet pipe 103. Even when the supply device shown in FIG. 5 is used, as a crushed material of the carrier-supported organometallic compound, a crushed material containing particles having a particle size of less than 0.84 mm obtained by crushing after being supported on a spherical carrier. By using the same effect as described above can be obtained.

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

Example 1
Trimethylindium (hereinafter referred to as “TMI”) is prepared as a solid organometallic compound at room temperature, and sponge titanium (particle size: 0.84 mm to 2.00 mm (manufactured by Toho Titanium)) and alumina sphere (α -Two types of alumina, diameter: 0.5 mm) were prepared. A mixture of 19 g of sponge titanium and 34 g of alumina spheres and 52 g of TMI was placed in a stainless steel container having an internal volume of 1600 ml, and the stainless steel container was heated to 105 ° C., which is equal to or higher than the melting point of TMI, to completely melt TMI. Thereafter, the stainless steel container was cooled to room temperature, and TMI was supported on a mixture of titanium sponge and alumina spheres. Next, this was crushed using a stainless steel tool such as a spatula, and further crushed so that the entire amount of the crushed material passed through a 4-mesh sieve. 103 g of crushed material was obtained.

  Here, when the obtained crushed material was sieved with a 20-mesh sieve, 15 g of the sieve passed through the sieve, and the remaining 88 g did not pass through the sieve. That is, the obtained crushed material contained 15 g of particles having a particle size of less than 0.84 mm and 88 g of particles having a larger particle size. In addition, the weight of TMI in the obtained crushed material is 50 g, and the ratio of the weight of TMI charged in the supply device to the weight of 52 g of TMI charged in the stainless steel container before carrying on the carrier (hereinafter referred to as “filling”). The yield was 96%.

  The obtained crushed material was filled into the two containers 1a and 1b of the supply device configured as shown in FIG. In this example, 103 g of crushed material having a total amount of TMI of 50 g was filled in two containers 1a and 1b in 70 g and 33 g, respectively.

  As the supply device, the containers 1a and 1b are both cylindrical, and the size of the container 1a on the side into which the carrier gas is introduced has an inner diameter of 55 mm, a height of 135 mm, and an internal volume of 302 ml, and the carrier gas is derived. The side container 1b had a size of an inner diameter of 17.5 mm, a height of 135 mm, and an internal volume of 31 ml. The communication pipe 5 was configured by combining straight pipes having an inner diameter of 7.5 mm. The containers 1a and 1b and the communication pipe 5 were made of stainless steel.

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

  The supply device is attached in a constant temperature bath maintained at normal pressure and 30 ° C., and argon gas is introduced as a carrier gas from the gas introduction pipe 2 into the container 1 a at a flow rate of 300 ml per minute, and is led out from the gas outlet pipe 3. A stable TMI supply test was performed by measuring the TMI concentration in the gas over time. As a result, the supply amount of TMI obtained from the gas outlet pipe 3 of the container 1b was about 0.42 g per hour, and the supply rate was stable up to a usage rate of 91%. Similarly, when a stable supply test of TMI was performed at an argon gas supply rate of 600 ml / min, the trimethylindium supply rate obtained from the gas outlet tube 3 was about 0.84 g / hour, and the supply rate was 89. % Use rate was stable.

(Example 2)
In Example 1, only alumina spheres (made of α-alumina, diameter: 0.5 mm) were used as the support, and the alumina spheres were prepared in the same manner as in Example 1 except that the weights of the used alumina spheres and TMI were changed. A crushed material of supported TMI was prepared, and a stable supply test of TMI was performed in the same manner as in Example 1 using the obtained crushed material. In preparing the crushed material, the weight of the alumina sphere used was 94 g, and the weight of TMI charged to carry the sphere on the alumina sphere was 52 g. The weight of the obtained crushed material was 144 g, and the weight of TMI was 50 g. That is, the packing yield was 96%. Moreover, when the obtained crushed material was sieved with a 20-mesh sieve, 19 g of the sieve passed through the sieve, and the remaining 125 g did not pass through the sieve. That is, the obtained crushed material contained 19 g having a particle size of less than 0.84 mm. In addition, the crushed material was filled in two containers 1a and 1b of the supply device separately in 107g and 37g, respectively.

  As a result of the stable supply test of TMI, when the supply amount of argon gas is 300 ml per minute, the supply amount of TMI obtained from the gas outlet tube 3 is 0.43 g / hour, and the supply rate is 93% usage rate It was stable until. When the supply amount of argon gas was 600 ml per minute, the supply amount of TMI obtained from the gas outlet tube 3 was 0.86 g per hour, and the supply rate was stable up to a usage rate of 91%. FIG. 6 shows a graph of the relationship between the usage rate of TMI and the supply amount obtained by the stable supply test of Example 2.

(Example 3)
In Example 2, except that the supply device used for the stable supply test of TMI was changed, a crushed product of alumina sphere-supported TMI was produced in the same manner as in Example 2, and the stable supply test was performed using the obtained crushed product. Went. The weight of the obtained crushed material was 144 g, of which the weight of TMI was 50 g (packing yield: 97%). Moreover, the obtained crushed material contained that whose particle size was less than 0.84 mm.

  The supply device used in Example 3 was the same as the supply device used in Example 1 in structure and material of each member, but the sizes of the containers 1a and 1b were different. Each of the containers 1a and 1b has a cylindrical shape, and the size of the container 1a on the side into which the carrier gas is introduced has an inner diameter of 55 mm, a height of 90 mm, and an internal volume of 195 ml. The size was an inner diameter of 17.5 mm, a height of 90 mm, and an internal volume of 20 ml. Along with the different sizes of the containers 1a and 1b, the two containers 1a and 1b were filled with crushed materials divided into 121 g and 23 g, respectively.

  As a result of the stable supply test of TMI, when the supply amount of argon gas is 300 ml per minute, the supply amount of TMI obtained from the gas outlet tube 3 is 0.41 g / hour, and the supply rate is 91% usage rate It was stable until. When the supply amount of argon gas was 600 ml per minute, the supply amount of TMI obtained from the gas outlet tube 3 was 0.82 g per hour, and the supply rate was stable up to a usage rate of 88%.

Example 4
In Example 2, except that the supply device used for the stable supply test of TMI was changed, a crushed product of alumina sphere-supported TMI was produced in the same manner as in Example 2, and the stable supply test was performed using the obtained crushed product. Went. The weight of the obtained crushed material was 144 g, of which the weight of TMI was 50 g (packing yield: 95%). Moreover, the obtained crushed material contained that whose particle size was less than 0.84 mm.

  The supply device used in Example 4 was the same as the supply device used in Example 1 in structure and material of each member, but the sizes of the containers 1a and 1b were different. Each of the containers 1a and 1b has a cylindrical shape, and the size of the container 1a on the side into which the carrier gas is introduced has an inner diameter of 55 mm, a height of 100 mm, and an internal volume of 219 ml. The size was an inner diameter of 23 mm, a height of 100 mm, and an internal volume of 39 ml. Along with the different sizes of the containers 1a and 1b, the two containers 1a and 1b were filled with 106 g and 38 g of crushed material, respectively.

  As a result of the stable supply test of TMI, when the supply amount of argon gas is 300 ml / min, the supply amount of TMI obtained from the gas outlet tube 3 is 0.43 g / hour, and the supply rate is 92% usage rate It was stable until. When the supply amount of argon gas was 600 ml per minute, the supply amount of TMI obtained from the gas outlet tube 3 was 0.86 g per hour, and the supply rate was stable up to a usage rate of 90%.

(Example 5)
In Example 1, the sponge titanium and alumina spheres as the carrier were respectively 38 g and 69 g in weight, and the weight of TMI charged to be carried on them was changed to 102 g. A crushed product of TMI with titanium / alumina spheres was obtained. The weight of the obtained crushed material was 207 g, of which the weight of TMI was 100 g (packing yield: 98%). Moreover, the obtained crushed material contained that whose particle size was less than 0.84 mm.

  Next, a stable supply test of TMI was performed in the same manner as in Example 1 using the obtained crushed material. However, in Example 5, since the weight of the obtained crushed material was 207 g, the two containers 1a and 1b of the supply device were filled with crushed material divided into 172 g and 35 g, respectively.

  As a result of the stable supply test of TMI, when the supply amount of argon gas is 300 ml / min, the supply amount of TMI obtained from the gas outlet tube 3 is 0.41 g / hour, and the supply rate is 94% of the usage rate It was stable until. When the supply amount of argon gas was 600 ml per minute, the supply amount of TMI obtained from the gas outlet tube 3 was 0.82 g per hour, and the supply rate was stable up to a usage rate of 92%.

(Example 6)
In Example 5, only alumina spheres (made of α-alumina, diameter: 0.5 mm) were used as the carrier, the weight of the used alumina spheres was 188 g, and the weight of TMI charged to be carried on the alumina spheres was A crushed product of alumina sphere-supported TMI was obtained in the same manner as in Example 5 except that the amount was 103 g. The weight of the obtained crushed material was 288 g, of which the weight of TMI was 100 g (packing yield: 97%). Moreover, the obtained crushed material contained that whose particle size was less than 0.84 mm.

  Next, a stable supply test of TMI was performed in the same manner as in Example 1 using the obtained crushed material. However, in Example 6, since the weight of the obtained crushed material was 288 g, the crushed material was divided into 252 g and 36 g, respectively, in the two containers 1a and 1b of the supply device.

  As a result of the stable supply test of TMI, when the supply amount of argon gas is 300 ml per minute, the supply amount of TMI obtained from the gas outlet tube 3 is 0.43 g / hour, and the supply rate is 95% of the usage rate It was stable until. When the supply amount of argon gas was 600 ml per minute, the supply amount of TMI obtained from the gas outlet tube 3 was 0.86 g per hour, and the supply rate was stable up to a usage rate of 93%.

(Example 7)
In Example 6, except that the weight of the alumina sphere used was 564 g, the weight of TMI charged to be carried on the alumina sphere was 306 g, and the supply device used for the TMI stable supply test was changed. In the same manner as in Example 6, a crushed product of alumina sphere-carrying TMI was obtained. The weight of the obtained crushed material was 864 g, of which the weight of TMI was 300 g (packing yield: 98%). Moreover, the obtained crushed material contained that whose particle size was less than 0.84 mm.

  The material used for the supply device used in Example 7 is the same as that of the supply device used in Example 1, but the size of each container 1a, 1b is different as shown in FIG. The filling port 4 was provided separately from the gas introduction pipe 2. Each of the containers 1a and 1b has a cylindrical shape, and the size of the container 1a on the side into which the carrier gas is introduced has an inner diameter of 83 mm, a height of 135 mm, and an internal volume of 690 ml. The size was an inner diameter of 23 mm, a height of 135 mm, and an internal volume of 53 ml. Further, inside the container 1a, a disperser (not shown) composed of a cone-shaped baffle plate having a recessed central portion is disposed below the gas introduction pipe 2. Along with the different sizes of the containers 1a and 1b, the two containers 1a and 1b were filled with crushed material divided into 802 g and 62 g, respectively.

  After filling the crushed material, 150 ml of the dispersion material 11 was filled only in the container 1a on the side where the carrier gas was introduced. As the dispersion material 11, an alumina sphere (α-alumina, diameter: 0.5 mm) was used.

  As a result of the stable supply test of TMI, when the supply amount of argon gas was 300 ml per minute, the supply amount of TMI obtained from the gas outlet tube 3 was 0.43 g / hour, and the supply rate was 89% usage rate It was stable until. When the supply amount of argon gas was 600 ml per minute, the supply amount of TMI obtained from the gas outlet tube 3 was 0.86 g per hour, and the supply rate was stable up to a usage rate of 87%.

(Example 8)
In Example 2, using only glass spheres (diameter: 0.5 mm) as a carrier and using a glass sphere having a weight of 61 g, the crushed material of glass sphere-supporting TMI was obtained in the same manner as in Example 2. Got. The weight of the obtained crushed material was 111 g, of which the weight of TMI was 50 g (packing yield: 96%). Moreover, when the obtained crushed material was sieved with a 20-mesh sieve, 18 g of them passed through the sieve, and the remaining 93 g did not pass through the sieve. That is, the obtained crushed material contained 18 g having a particle size of less than 0.84 mm.

  Next, a stable supply test of TMI was performed in the same manner as in Example 1 using the obtained crushed material. However, in Example 8, since the weight of the obtained crushed material was 111 g, the two containers 1a and 1b of the supply apparatus were filled with the crushed material divided into 83 g and 28 g, respectively. After filling the crushed material, 100 ml of the dispersion material 11 was filled only in the container 1a on the side where the carrier gas was introduced. As the dispersion material 11, a glass sphere (diameter: 0.5 mm) was used.

  As a result of the stable supply test of TMI, when the supply amount of argon gas is 300 ml per minute, the supply amount of TMI obtained from the gas outlet tube 3 is 0.43 g / hour, and the supply rate is 90% usage rate It was stable until. When the supply amount of argon gas was 600 ml per minute, the supply amount of TMI obtained from the gas outlet tube 3 was 0.86 g per hour, and the supply rate was stable up to a usage rate of 87%.

Example 9
In Example 2, the alumina sphere-supported TMI was crushed in the same manner as in Example 2, except that the weight of the alumina sphere used was 60 g and the weight of TMI charged to support the alumina sphere was 31 g. Got. The weight of the obtained crushed material was 90 g, and the weight of TMI was 30 g (packing yield: 97%). Moreover, the obtained crushed material contained that whose particle size was less than 0.84 mm.

  Next, a stable supply test of TMI was performed in the same manner as in Example 1 except that the crushed material was used and the temperature was 25 ° C. However, in Example 9, a single container 101 having a cylindrical portion and a cone portion formed in a funnel shape below the cylindrical portion as shown in FIG. 4 was used. Specifically, the cylindrical part has a height of 96 mm, the inner diameter is 46 mm, the cone part has a height of 32 mm, the upper end has an inner diameter of 46 mm, and the lower end has an inner diameter of 16 mm. Was 192 ml. The container 101 was filled with 90 g of crushed material. After filling the crushed material, 79 ml of the dispersion material 111 was filled in the container 101. As the dispersion material 111, alumina spheres (α-alumina, diameter: 0.5 mm) were used.

  As a result of the stable supply test of TMI, when the supply amount of argon gas is 600 ml per minute, the supply amount of TMI obtained from the gas outlet tube 103 is 0.64 g / hour, and the supply rate is 84% usage rate. It was stable until. In this example, a stable supply test was not performed when the argon gas supply rate was 300 ml per minute.

(Example 10)
In Example 9, a crushed glass sphere-supported TMI was obtained in the same manner as in Example 9 except that the support was changed to 40 g of glass spheres (diameter: 0.5 mm). The weight of the obtained crushed material was 70 g, and the weight of TMI was 30 g (packing yield: 97%). Moreover, when the obtained crushed material was sieved with a 20-mesh sieve, the obtained crushed material contained particles having a particle size of less than 0.84 mm.

  Next, the obtained crushed material and dispersion material were filled in the single container 101 (see FIG. 4) used in Example 9, and a stable supply test of TMI was performed in the same manner as in Example 9. The filling amount of the crushed material into the container 101 was 70 g. Further, as the dispersion material 111, glass spheres (diameter: 0.5 mm) were used, and the filling amount was 79 ml.

  As a result of the stable supply test of TMI, when the supply amount of argon gas is 600 ml per minute, the supply amount of TMI obtained from the gas outlet tube 103 is 0.64 g / hour, and the supply rate is 87% usage rate It was stable until.

(Example 11)
In Example 2, except that the supply device used for the stable supply test of TMI was changed, a crushed product of alumina sphere-supported TMI was produced in the same manner as in Example 2, and the stable supply test was performed using the obtained crushed product. Was done. The weight of the obtained crushed material was 145 g, of which the weight of TMI was 50 g (packing yield: 97%). Moreover, the obtained crushed material contained that whose particle size was less than 0.84 mm.

  For the stable supply test, a supply apparatus having a single container 101 as shown in FIG. 5 was used. The container 101 used had a lower diameter smaller than the upper part, the upper inner diameter was 69 mm, the lower inner diameter was 20 mm, the height was 154 mm, and the internal volume was 300 ml. Further, the disperser 105 disposed in the lower part of the container 101 was made of stainless steel, and the hole diameter was 90 μm. The filling amount of the crushed material into the container 101 was 145 g, alumina spheres (α-alumina, diameter: 0.5 mm) were used as the dispersion material, and the filling amount was 150 ml.

  As a result of the stable supply test of TMI, when the supply amount of argon gas is 300 ml per minute, the supply amount of TMI obtained from the gas outlet tube 103 is 0.44 g / hour, and the supply rate is 88% usage rate It was stable until. When the supply amount of argon gas was 600 ml per minute, the supply amount of TMI obtained from the gas outlet tube 103 was 0.88 g per hour, and the supply rate was stable up to a usage rate of 87%.

(Comparative Example 1)
In Example 1, only sponge titanium (particle size: 0.84 mm to 2.00 mm, manufactured by Toho Titanium Co., Ltd.) was used as a carrier, and a crushed product of sponge titanium-carrying TMI obtained by sieving with a 4-mesh sieve. Was further sieved with a 20-mesh sieve, and a crushed product of sponge titanium-carrying TMI was obtained in the same manner as in Example 1 except that the crushed product having a particle size of less than 0.84 mm passed through the sieve was removed. The weight of the titanium sponge used was 75 g, the weight of the TMI charged for supporting the titanium sponge was 62 g, and the obtained crushed material had a particle size of 0.84 mm to 4.76 mm and a weight of 125 g. The weight of TMI in the crushed material was 50 g (filling yield: 81%).

  Next, a stable supply test of TMI was performed in the same manner as in Example 1 using the obtained crushed material. However, in Comparative Example 1, since the weight of the obtained crushed material was 125 g, the two containers 1a and 1b of the supply device were filled with crushed material divided into 92 g and 33 g, respectively.

  As a result of the stable supply test of TMI, when the supply amount of argon gas is 300 ml per minute, the supply amount of TMI obtained from the gas outlet tube 3 is 0.42 g per hour, and the supply rate is 91% of the usage rate It was stable until. When the supply amount of argon gas was 600 ml per minute, the supply amount of TMI obtained from the gas outlet tube 3 was 0.84 g per hour, and the supply rate was stable up to a usage rate of 89%.

(Comparative Example 2)
In Comparative Example 1, the support was changed to an alumina sphere (made of α-alumina, diameter: 0.5 mm), the weight thereof was set to 108 g, and the weight of TMI charged for supporting the alumina sphere was changed to 66 g. In the same manner as in Comparative Example 1, a crushed product of alumina sphere-supported TMI having a particle size of 0.84 mm to 4.76 mm was obtained. The weight of the obtained crushed material was 148 g, and the weight of TMI was 50 g (packing yield: 76%).

  Next, using the obtained crushed material, a stable supply test of TMI was conducted in the same manner as in Example 1. However, in Comparative Example 2, because the weight of the obtained crushed material was 148 g, the two containers 1a and 1b of the supply device were filled with the crushed material separately into 111 g and 37 g, respectively.

  As a result of the stable supply test of TMI, when the supply amount of argon gas is 300 ml per minute, the supply amount of TMI obtained from the gas outlet tube 3 is 0.43 g / hour, and the supply rate is 93% usage rate It was stable until. When the supply amount of argon gas was 600 ml per minute, the supply amount of TMI obtained from the gas outlet tube 3 was 0.86 g per hour, and the supply rate was stable up to a usage rate of 91%.

(Comparative Example 3)
In Example 2, after filling the crushed alumina sphere-supported TMI, the container 1a on the side into which the carrier gas was introduced was not filled with the dispersion material, and the TMI was stabilized in the same manner as in Example 2. A supply test was conducted. However, in Comparative Example 3, the crushed material was divided into 106 g and 38 g, respectively, in the two containers 1a and 1b of the supply device.

  As a result of the TMI stable supply test, when the supply amount of argon gas is 300 ml per minute, the supply amount of TMI obtained from the gas outlet tube 3 is 0.43 g / hour, and the supply rate is 82% of the usage rate. It was only stable until. Further, when the supply amount of argon gas is 600 ml per minute, the supply amount of TMI obtained from the gas outlet tube 3 is 0.86 g per hour, and the supply rate is stable only up to 80% usage rate. It was.

(Comparative Example 4)
In Example 2, the same method as in Example 2 except that only sponge titanium (particle size: 0.84 mm to 2.00 mm (manufactured by Toho Titanium Co.)) was used as the carrier, and the weight of sponge titanium used was 54 g. The crushed material of sponge titanium carrying TMI was obtained. The weight of the obtained crushed material was 104 g, and the weight of TMI was 50 g (packing yield: 96%). Moreover, when the obtained crushed material was sieved with a 20 mesh sieve, 10 g of the sieve passed through the sieve, and the remaining 94 g did not pass through the sieve. That is, the obtained crushed material contained 10 g having a particle size of less than 0.84 mm.

  Next, a stable supply test of TMI was performed in the same manner as in Example 1 using the obtained crushed material. However, in Comparative Example 4, since the weight of the obtained crushed material was 104 g, the two containers 1a and 1b of the supply device were filled with 71 g and 33 g of crushed material, respectively.

  As a result of the stable supply test of TMI, when the supply amount of argon gas is 300 ml per minute, the supply amount of TMI obtained from the gas outlet tube 3 is 0.44 g per hour, and the supply rate is 78% of the usage rate It was only stable until. Further, when the supply amount of argon gas is 600 ml per minute, the supply amount of TMI obtained from the gas outlet tube 3 is 0.88 g per hour, and the supply rate is stable only up to a usage rate of 72%. It was.

(Comparative Example 5)
In Comparative Example 4, the TMI stable supply test was performed in the same manner as in Comparative Example 4 except that the dispersion material was not filled in the container 1a on the side into which the carrier gas was introduced after filling the crushed material of the titanium sponge carrying TMI. Went.

  As a result of the stable supply test of TMI, when the supply amount of argon gas is 300 ml / min, the supply amount of TMI obtained from the gas outlet tube 3 is 0.42 g / hour, and the supply rate is 65% It was only stable until. Further, when the supply amount of argon gas is 600 ml per minute, the supply amount of TMI obtained from the gas outlet tube 3 is 0.84 g per hour, and the supply rate is stable only up to a usage rate of 62%. It was.

(Comparative Example 6)
In Comparative Example 4, a crushed product of sponge titanium-carrying TMI was obtained in the same manner as in Comparative Example 4 except that the weight of TMI was 31 g and the weight of sponge titanium as a carrier was 35 g. The weight of the obtained crushed material was 65 g, of which the weight of TMI was 30 g (packing yield: 97%). Moreover, the obtained crushed material contained that whose particle size was less than 0.84 mm.

  Next, the obtained crushed material and dispersion material were filled in the single container 101 (see FIG. 4) used in Example 9, and a stable supply test of TMI was performed in the same manner as in Example 9. The amount of crushed material in the container 101 was 65 g. Moreover, as the dispersion material 111, alumina spheres (α-alumina, diameter: 0.5 mm) were used, and the filling amount was 79 ml.

  As a result of the stable supply test of TMI, when the supply amount of argon gas is 600 ml per minute, the supply amount of TMI obtained from the gas outlet tube 103 is 0.60 g / hour, and the supply rate is 67% usage rate. It was only stable until.

(Comparative Example 7)
In Example 11, a sponge titanium-carrying TMI crushed material was obtained in the same manner as in Example 11 except that sponge titanium (particle size: 0.84 mm to 2.00 m, manufactured by Toho Titanium Co., Ltd.) was used as the carrier. It was. The weight of the obtained crushed material was 103 g, and the weight of TMI was 50 g (packing yield: 96%). Moreover, the obtained crushed material contained that whose particle size was less than 0.84 mm.

  Next, the obtained crushed material and dispersion material were filled into a supply device (see FIG. 5) having a single container 101 used in Example 11, and a stable supply test of TMI was performed in the same manner as in Example 11. . The filling amount of the crushed material into the container 101 was 103 g. Further, alumina spheres (α-alumina, diameter: 0.5 mm) were used as the dispersing material, and the filling amount was 150 ml.

  As a result of the stable supply test of TMI, when the supply amount of argon gas is 300 ml / min, the supply amount of TMI obtained from the gas outlet tube 103 is 0.44 g / hour, and the supply rate is 74% usage rate. It was only stable until. Further, when the supply amount of argon gas is 600 ml per minute, the supply amount of TMI obtained from the gas outlet tube 103 is 0.88 g per hour, and the supply rate is stable only up to a usage rate of 70%. It was.

  Table 1 summarizes main test conditions and test results of Examples 1 to 11 and Comparative Examples 1 to 7 described above.

  From Table 1, Examples 1-11 compared with Comparative Examples 1-2, although the stable use ratio of TMI is equivalent, the filling yield has improved 10% or more, and the synthetic | combination of an organometallic compound It can be seen that the utilization efficiency is improved. Moreover, although Comparative Examples 3-7 has achieved the packing yield equivalent to Examples 1-11, the stable use ratio of TMI is falling compared with Examples 1-11 greatly.

1a, 1b, 101 Container 2, 102 Gas introduction pipe 3, 103 Gas outlet pipe 4, 104 Filling port 5 Communication pipe 10, 110 Organometallic compound 11, 111 Dispersant 105 Disperser

Claims (4)

A supply device for supplying a solid organometallic compound accompanying a carrier gas at room temperature, comprising container means having a carrier gas inlet and outlet,
An organometallic compound filled in the container means;
In the container means, a dispersion material filled in the upstream side of the organometallic compound in the flow direction of the carrier gas and dispersing the carrier gas introduced from the inlet,
Have
The organometallic compound is crushed after being supported on a spherical carrier, and is filled in the container means as a crushed material obtained without sieving those having a particle size of less than 0.84 mm. Feeding device. The container means includes
A column-type first container in which the introduction port is provided at the top and filled with the crushed material;
A column-type second container in which the outlet is provided at the top and filled with the crushed material;
A connecting member that communicates the inside of the first container and the inside of the second container at its lower end;
The supply device according to claim 1.   The supply device according to claim 2, wherein the dispersion material is filled in the first container. The supply device according to claim 3, wherein the dispersion material is packed in layers on the crushed material so as to cover the crushed material.

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