JP5655874B2 - Support-supported organometallic compound for vapor phase growth, production method thereof, and organometallic compound filling device for vapor phase growth filled with the compound - Google Patents

Description

  The present invention relates to a carrier-supporting organometallic compound for vapor phase growth, a process for producing the same, and an apparatus for filling an organometallic compound for vapor phase growth filled with the compound. An organometallic compound is a compound useful as a raw material for electronic industrial materials such as compound semiconductors.

  Conventionally, as a vapor-grown carrier-supported organometallic compound and its production method, and as a vapor-grown organometallic compound filling apparatus filled with the compound, for example, an inert carrier such as an alumina sphere is coated with trimethylindium, A method of supplying an organometallic compound using an organometallic compound filling apparatus for vapor phase growth formed by filling it is disclosed (for example, see Patent Document 1). However, this method has a problem that it is an effective method only when a supply device having a carrier gas inlet at the top and a carrier gas outlet at the bottom is used. A method and apparatus for supplying compounds has been desired.

Japanese Patent No. 2651530

  An object of the present invention is to solve the above-mentioned problems, and does not depend on a supply device, and can stably supply an organometallic compound at a constant concentration for a long period of time. Another object of the present invention is to provide an organic metal compound filling apparatus for vapor phase growth filled with the compound.

It is an object of the present invention to provide a carrier-supported organometallic for vapor phase growth obtained by melting and supporting the organometallic compound on a carrier inert to the organometallic compound for vapor phase growth that is solid at room temperature, and then crushing and sieving the organometallic compound. Solved by a carrier-supported organometallic compound for vapor phase growth and a process for producing the same, characterized in that the compound does not include a carrier-supported organometallic compound having a particle size of greater than 4.76 mm and a particle size of less than 0.84 mm .

Another object of the present invention is to provide an organic metal compound filling apparatus for vapor phase growth comprising a container which contains a solid organic metal compound for vapor phase growth at room temperature and sublimates the organic metal compound for vapor phase growth. Also provided with an organometallic compound filling apparatus for vapor phase growth characterized in that a carrier gas introduction port and a carrier gas outlet port are installed in the container, and the container-supported organometallic compound of the present invention is filled in the container. Solved.
Another object of the present invention is a method for supplying a carrier-supported organometallic compound for vapor phase growth, which has a carrier gas inlet and a carrier gas discharge port, and also comprises the carrier-supported organometallic compound of the present invention described above. This can also be solved by a method for supplying a carrier-supported organometallic compound for vapor phase growth using a container filled with a gas.

  According to the present invention, a vapor-phase-grown carrier-supported organometallic compound capable of stably supplying an organometallic compound at a constant concentration for a long period of time without depending on a supply apparatus, a process for producing the same, and a gas filled with the compound. An organic metal compound filling apparatus for phase growth can be provided.

It is a schematic cross section which shows the filling apparatus used in the present Example 2 and Comparative Example 2. It is a schematic cross section which shows the filling apparatus used by the present Example 4, 8, 10, 12, 14 and the comparative examples 4 and 6. FIG. It is a schematic cross section which shows the filling apparatus used in the present Example 6.

  Examples of the organic metal compound for vapor phase growth that is solid at room temperature used in the present invention include lithium compounds such as tert-butyllithium; trimethylindium, dimethylchloroindium, cyclopentadienylindium, trimethylindium / trimethylarsine adduct, Organic indium compounds such as trimethylindium and trimethylphosphine adducts; Organic zinc compounds such as ethyl zinc iodide, ethylcyclopentadienyl zinc and cyclopentadienyl zinc; Organoaluminum compounds such as methyldichloroaluminum and triphenylaluminum; Methyldichlorogallium Organic gallium compounds such as dimethylchlorogallium and dimethylbromogallium; Magnesium compounds such as bis (cyclopentadienyl) magnesium; Triphenylbisma Bismuth compounds such as bis; 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 bis (acetylacetonato) strontium and dipivaloylmethanatostrontium; copper compounds such as bis (acetylacetonato) copper and dipivaloylmethanatocopper; bis (acetylacetonato) calcium and dipivalo Calcium compounds such as ilmethanatocalcium; yttrium compounds such as dipivaloylmethanatoribium.

  The carrier used in the present invention is not particularly limited as long as it is inert to the organometallic compound for vapor phase growth that is solid at room temperature. For example, alumina, silica, mullite, glassy carbon, graphite, potassium titanate, etc. Sponge titanium, quartz, silicon nitride, boron nitride, silicon carbide, stainless steel, aluminum, nickel, 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. Further, the shape of the carrier is not particularly limited, and those having 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 are used.

  The specific surface area of the carrier is preferably one having fine irregularities of about 100 to 2000 μm on the surface of the carrier or one having a large number of pores (voids) in the carrier itself. Specific examples of such a carrier include alumina hole packing, Raschig ring, Helipak, Dickson packing, Fenceke, sponge titanium, stainless sintered element, glass wool and the like.

  The production of an organometallic compound for vapor phase growth that does not contain a carrier-supporting organometallic compound having a particle size of less than 0.84 mm according to the present invention includes, for example, an inert carrier for an organometallic compound and an organometallic compound in an inert gas atmosphere. After mixing, the organic metal compound is completely melted by heating to above the melting point of the organometallic compound, and then cooled and supported, followed by crushing and sieving.

  The amount of the organometallic compound charged during the production is preferably 0.3 to 2.6 g, more preferably 0.5 to 1.5 g, with respect to 1 ml of the carrier.

  An organometallic compound filling apparatus for vapor phase growth applicable to the present invention has a carrier gas introduction port and a carrier gas outlet port installed in the container, and a carrier-supported organometallic compound having a particle diameter of less than 0.84 mm in the container. If the organometallic compound for vapor phase growth not contained is filled, the shape and size of the filling apparatus are not particularly limited, and a conventionally known filling apparatus can be used as it is.

  Also, the filling method of the organometallic compound for vapor phase growth into the filling device is not particularly limited as long as it is a commonly used method. For example, the filling port of the filling device can be used in an inert gas atmosphere. Then, it is performed by a method such as charging as it is.

  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 carrier gas outlet 3 was measured with an ultrasonic gas concentration meter (trade name: Piezocon (manufactured by Lorex)).

Example 1 (Synthesis of helium-pack-supported trimethylindium having a particle size of 0.84 to 4.76 mm)
In a Teflon (registered trademark) container with an internal volume of 250 ml, add 38 ml of Helipak (1.3 mm x 2.5 mm x 2.3 mm (manufactured by Tokyo Special Wire Mesh)) and 33 g of trimethylindium, and heat to 90 ° C to completely melt trimethylindium. After cooling to room temperature, trimethylindium was supported on the helipac, and then crushed with a spatula and sieved with a 4 mesh and 20 mesh sieve to obtain 71 g of helipack-supported trimethylindium having a particle size of 0.84 to 4.76 mm. Obtained.

Example 2 (Production of Trimethylindium Filling Device for Vapor Phase Growth Filled with Helipack-Supported Trimethylindium with a Particle Size of 0.84 to 4.76 mm)
Stainless steel organometallic compound for vapor phase growth in a lower capillary vessel (upper inner diameter: 69 mmφ, lower inner diameter: 20 mmφ) with a carrier gas inlet 1 and a carrier gas outlet 2 as shown in FIG. 1 in a nitrogen atmosphere. The supply device was filled with 71 g of helium-pack-supported trimethylindium having a particle diameter of 0.84 to 4.76 mm obtained in Example 1 through the filling port 3.

Example 3 (Trimethylindium supply stability test)
As a result of flowing argon gas from the carrier gas inlet 1 at 300 ml / min, the supply amount of trimethylindium was 0.4 g / h, and the supply rate was stable up to 77% of the usage rate.

Comparative Example 1 (Synthesis of helium-pack-supported trimethylindium having a particle size of 0.25 to 4.76 mm)
In Example 1, sieving was performed with a 4-mesh and 60-mesh sieve to obtain 73 g of helipack-supporting trimethylindium having a particle size of 0.25 to 4.76 mm.

Comparative Example 2 (Making a Trimethylindium Filling Device for Vapor Deposition Filled with Helipack-Supported Trimethylindium with a Particle Size of 0.25 to 4.76 mm)
In Example 2, except for changing the helipack-supporting trimethylindium having a particle diameter of 0.84 to 4.76 mm obtained in Example 1, and using the helipack-supporting trimethylindium having a particle diameter of 0.25 to 4.76 mm obtained in Comparative Example 1 was used. In the same manner as in Example 2, 73 g of helipack-supporting trimethylindium having a particle diameter of 0.25 to 4.76 mm obtained in Comparative Example 1 was filled through the filling port 3.

Comparative Example 3 (Trimethylindium supply stability test)
As a result of flowing argon gas from the carrier gas inlet 1 at 300 ml / min, the supply amount of trimethylindium was 0.4 g / h, and the supply rate was stable only up to 60% of the usage rate.

Example 4 (Production of Trimethylindium Filling Device for Vapor Deposition Filled with Helipack-Supported Trimethylindium of Particle Size 0.84 to 4.76 mm)
Stainless steel organometallic compound for vapor phase growth in a lower capillary vessel (upper inner diameter: 69 mmφ, lower inner diameter: 20 mmφ) in which a carrier gas inlet 1 and a carrier gas outlet 2 are installed as shown in FIG. 2 in a nitrogen atmosphere. The feeding device was filled with 71 g of helipack-supporting trimethylindium having a particle diameter of 0.84 to 4.76 mm obtained in the same manner as in Example 1 through the filling port 3.

Example 5 (Trimethylindium supply stability test)
As a result of flowing argon gas at 300 ml / min from the carrier gas inlet 1, the supply amount of trimethylindium was 0.4 g / h, and the supply rate was stable up to 75% of the usage rate.

Example 6 (Preparation of a trimethylindium filling apparatus for vapor phase growth filled with helium-pack-supported trimethylindium having a particle size of 0.84 to 4.76 mm)
Implemented in a stainless steel organometallic compound supply device for vapor phase growth in a lower conical container (upper inner diameter: 54 mmφ) with a carrier gas inlet 1 and a carrier gas outlet 2 as shown in FIG. 3 in a nitrogen atmosphere. 71 g of trimethylindium supported on helipac having a particle diameter of 0.84 to 4.76 mm obtained in the same manner as in Example 1 was filled through the filling port 3.

Example 7 (Trimethylindium supply stability test)
As a result of flowing argon gas at 300 ml / min from the carrier gas inlet 1, the supply amount of trimethylindium was 0.4 g / h, and the supply rate was stable up to 72% of the usage rate.

Comparative Example 4 (Preparation of a trimethylindium filling apparatus for vapor phase growth filled with trimethylindium supporting Helipac having a particle size of 0.25 to 4.76 mm)
Stainless steel organometallic compound for vapor phase growth in a lower capillary vessel (upper inner diameter: 69 mmφ, lower inner diameter: 20 mmφ) in which a carrier gas inlet 1 and a carrier gas outlet 2 are installed as shown in FIG. 2 in a nitrogen atmosphere. The supply device was filled with 71 g of helium-pack-supported trimethylindium having a particle size of 0.25 to 4.76 mm obtained in the same manner as in Comparative Example 1 through the filling port 3.

Comparative Example 5 (Trimethylindium supply stability test)
As a result of flowing argon gas from the carrier gas inlet 1 at 300 ml / min, the supply amount of trimethylindium was 0.4 g / h, and the supply rate was stable only to 62% of the usage rate.

Comparative Example 6 (Making a Trimethylindium Filling Device for Vapor Deposition Filled with Helipack-Supported Trimethylindium with a Particle Size of 4.76mm or Less)
In Example 1, except that the operation of sieving with a 4-mesh and 20-mesh sieve was changed, and only a 4-mesh sieve was used, and the particle size was 4.76 mm or less. The helipak-supported trimethylindium (71 g) was filled through the filling port 3 into the stainless steel organometallic compound supply apparatus for vapor phase growth shown in FIG.

Comparative Example 7 (Trimethylindium supply stability test)
As a result of flowing argon gas at 300 ml / min from the carrier gas inlet 1, the supply amount of trimethylindium was 0.4 g / h, and the supply rate was stable only to 45% of the usage rate.

Example 8 (Preparation of a trimethylindium filling apparatus for vapor phase growth filled with trimethylindium carrying titanium sponge having a particle diameter of 0.84 to 4.76 mm)
In Example 1, obtained in the same manner as in Example 1 except that sponge titanium (particle size: 0.84 to 2.00 mm (manufactured by Toho Titanium)) was used instead of the helipack used as a carrier for supporting trimethylindium. 75 g of trimethylindium supported on sponge titanium having a particle diameter of 0.84 to 4.76 mm was filled through the filling port 3 into the stainless steel organometallic compound supply apparatus for vapor phase growth shown in FIG.

Example 9 (Trimethylindium supply stability test)
As a result of flowing argon gas at 300 ml / min from the carrier gas inlet 1, the supply amount of trimethylindium was 0.4 g / h, and the supply rate was stable up to 75% of the usage rate.

Example 10 (Preparation of a trimethylindium filling apparatus for vapor phase growth filled with Dickson packing-supporting trimethylindium having a particle size of 0.84 to 4.76 mm)
In Example 1, except that the Dipson packing (φ3.0 mm, height 3.0 mm (manufactured by Okutani Wire Mesh Co., Ltd.)) was used instead of the helipack used as a carrier for supporting trimethylindium, the same as in Example 1 The stainless steel organometallic compound supply apparatus for vapor phase growth shown in FIG. 2 used in Example 4 was filled through the filling port 3 with 53 g of Dickson packing-supported trimethylindium having a particle diameter of 0.84 to 4.76 mm obtained by the method.

Example 11 (Trimethylindium supply stability test)
As a result of flowing argon gas at 300 ml / min from the carrier gas inlet 1, the supply amount of trimethylindium was 0.4 g / h, and the supply rate was stable up to 75% of the usage rate.

Example 12 (Production of Trimethylindium Filling Device for Vapor Phase Growth Filled with Teflon (R) Raschig Ring-Supporting Trimethylindium of Particle Size 0.84 to 4.76 mm)
In Example 1, the Helipak used as a carrier for supporting trimethylindium was changed and a Teflon (registered trademark) Raschig ring (φ2.0 mm, height 4.0 mm) was used. The obtained Teflon (registered trademark) Raschig ring-supporting trimethylindium (53 g) having a particle diameter of 0.84 to 4.76 mm was passed through the filling port 3 to the stainless steel organic metal compound supply device for vapor phase growth shown in FIG. Filled.

Example 13 (Trimethylindium supply stability test)
As a result of flowing argon gas at 300 ml / min from the carrier gas inlet 1, the supply amount of trimethylindium was 0.4 g / h, and the supply rate was stable up to 72% of the usage rate.

Example 14 (Preparation of a trimethylindium filling apparatus for vapor phase growth filled with SUS sphere-supporting trimethylindium having a particle diameter of 0.84 to 4.76 mm)
A particle size of 0.84 to 4.76 mm obtained in the same manner as in Example 1 except that the SUS ball (φ2.0 mm) was used in place of the helipack used as a carrier for supporting trimethylindium in Example 1. SUS sphere-supporting trimethylindium (212 g) was filled through the filling port 3 into the stainless steel organometallic compound supply apparatus for vapor phase growth shown in FIG.

Example 15 (Trimethylindium supply stability test)
As a result of flowing argon gas at 300 ml / min from the carrier gas inlet 1, the supply amount of trimethylindium was 0.4 g / h, and the supply rate was stable up to 72% of the usage rate.

  The present invention relates to a carrier-supporting organometallic compound for vapor phase growth, a process for producing the same, and an apparatus for filling an organometallic compound for vapor phase growth filled with the compound. An organometallic compound is a compound useful as a raw material for electronic industrial materials such as compound semiconductors.

1 Carrier gas inlet 2 Carrier gas outlet 3 Filling port

Claims (6)

A carrier-supported organometallic compound for vapor phase growth obtained by melting and supporting the trimethylindium on a carrier inert to trimethylindium which is a solid-state organometallic compound for vapor phase growth at room temperature, and then crushing and sieving. The vapor-phase growth carrier-supported metal compound is characterized by being sieved to a size that passes through a 4-mesh sieve and does not pass through a 20-mesh sieve . .   The carrier-supported organometallic compound for vapor phase growth according to claim 1, wherein the content relative to 1 ml of the carrier is 0.3 to 2.6 g.   The carrier-supported organometallic compound for vapor phase growth according to claim 1 or 2, wherein the carrier is one or more carriers selected from the group consisting of Helipak, sponge titanium, Dixon packing, Raschig rings and SUS spheres. An organic metal compound filling apparatus for vapor phase growth comprising a container for containing a metal organic compound for vapor phase growth that is solid at room temperature and sublimating the organometallic compound for vapor phase growth. An organic metal compound filling apparatus for vapor phase growth, characterized in that a lead-out port is installed and the vessel-supported organic metal compound for vapor phase growth according to any one of claims 1 to 3 is filled in the container. After mixing trimethylindium and a carrier inert to trimethylindium , the mixture is heated to melt the organometallic compound, then cooled and supported, crushed , and passed through a 4-mesh sieve and 20 mesh. The method for producing a carrier-supporting organometallic compound for vapor phase growth according to any one of claims 1 to 3 , wherein the sieving is performed to a size that does not pass through a sieve . A method for supplying a carrier-supported organometallic compound for vapor phase growth, comprising a carrier gas inlet and a carrier gas outlet, and comprising a carrier-supported organometal for vapor phase growth according to any one of claims 1 to 3. A method for supplying a carrier-supporting organometallic compound for vapor phase growth, using a container filled with the compound.

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