JPH06151311A - Solid organic metal compound supply equipment in organic metal vapor growth method - Google Patents

Abstract

PURPOSE:To stabilize the supply speed of solid organic metal, by using a column type vessel when a filling vessel is uniformly filled with solid organic metal compound, its carrier and filler. CONSTITUTION:A column type vessel 1 made of glass whose inner diameter and height are 30mm and 200mm, respectively, is filled with mixture of 50g trymethyl indium and 50g stainless 'helipack'. The vessel 1 is dipped in a thermostatic chamber at 25 deg.C. A carrier gas feeding outlet 4 is connected with a liquid nitrogen trap for TMI capturing use. Piping which connects the feeding outlet 4 with the liquid nitrogen trap is heated at 35 deg.C, in order to prevent TMI from depositing in the piping. The supply speed of TMI is stable until the application percentage is 70wt.%. Thereby solid organic metal compound can be supplied to a vapor growth equipment with excellent reproducibility.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a solid metalorganic compound supply device for metalorganic vapor phase epitaxy.

[0002]

2. Description of the Related Art In recent years,
In the production of semiconductor lasers and the like, a vapor phase growth method (MOCVD method) using an organic metal compound has been adopted. In addition, MO for researching high-temperature superconductor thin films
The CVD method is beginning to be used. Along with this, the use of organic metals that are solid at room temperature is increasing, and various methods for stabilizing the supply rate of these have been proposed.

For example, as shown in Japanese Patent Application Laid-Open No. 1-265511, an organic metal supported on an inert carrier, and an inert filler as disclosed in Japanese Patent Application Laid-Open No. 2-69389. There has been a proposal to stabilize the supply rate of solid organometallic by mixing. However, the filling container proposed above is shown in FIG.
As shown in (1), the tube (2) was inserted into the container (1) as a gas outlet, and the shape of the container was complicated, so that solid filling was likely to be non-uniform and reproducibility was poor. In the figure, (6) indicates a filter. Furthermore, when the filling amount of the solid organic metal increased, the container became large, and the filling state became more and more uneven. As a result, the stability of the supply rate of the solid organic metal tends to decrease as the filling amount increases.

[0004]

As a result of various studies in view of this, the present invention has developed a device capable of stably supplying a solid organic metal.

That is, according to the present invention, the shape of a container for filling an organic metal which is solid at room temperature, a mixture of the organic metal and an inert filler, or a mixture of the organic metal and an inert carrier carried by an inert carrier is shown in FIG.
As shown in Fig. 4, a column-type straight tube was used, and by removing the carrier gas derivation tube in the conventional filling container, the contact resistance inside the container was made uniform and reproducible filling was possible. The present invention relates to a solid organometallic compound supply device in the growth method. When the filling amount of the solid organic metal increases, as shown in FIGS. 3 (a) and 3 (b), a column-shaped container having an appropriate diameter that can be uniformly filled is connected to obtain a stable supply rate. An object of the present invention is to provide a solid organometallic compound supply device in a metal vapor phase growth method.

The present invention will be described in more detail below. The column-type packing container used in the solid organometallic compound supply device of the present invention may have any shape as long as it has a column shape such as a cylinder, a triangular cylinder, a square cylinder, and a hexagonal cylinder, but is preferably a cylindrical shape. And, for example, as shown in FIG. 2, a filling container (1)
The carrier gas introduction port (3) is located at the upper part of the container, and the introduction angle is not particularly limited. The carrier gas outlet (4) is located in the lower part of the container and is directly led to the outside. The inner diameter of the container is not particularly limited, but an appropriate size can be selected depending on the shape of the solid organic metal to be filled, the carrier, and the filler.

When the filling amount of the solid organic metal increases, the column type filling container is connected instead of enlarging the container as in the conventional case. The connection method is as shown in FIG. 3 (a), in which the carrier gas outlet (4) is connected in series to the inlet (3) of the next container (1 ′), and as shown in FIG. 3 (b). There is a method of connecting containers in parallel. When connected in parallel, the resistance to the carrier gas in each filling container is less likely to be uniform, so it is necessary to install a flow meter (5) etc. in front of the carrier gas inlet of each filling container to control the flow of the carrier gas. There is.

The solid organometallic compound used in the present invention includes an alkyl metal compound, a cyclopentadienyl compound, a β-diketone complex, an adduct compound, and the like. Specifically, trimethylindium, dimethylchloroindium, triphenylaluminum. , Alkyl metal compounds such as triphenylbismuth, tert-butyllithium, cyclopentadienylindium, cyclopentadienylmagnesium, cyclopentadienyl compounds such as cyclopentadienylmanganese, barium acetylacetonate complex, strontium acetylacetonate Complex, copper acetylacetonate complex, calcium acetylacetonate complex, barium dipivaloyl methanate complex, strontium dipivaloyl methanate complex, copper dipivaloyl methanate complex, yt Potassium dipivaloylmethanato complex, calcium dipivaloylmethanato β-diketone complexes such as complexes, trimethyl indium trimethyl arsine adduct, trimethyl indium-trimethyl phosphine adduct, barium dipivaloylmethanate,
An adduct compound such as a 1,10-phenanthroline adduct may be mentioned.

[0009]

The present invention will be described below with reference to examples.

(Example 1) Inner diameter 30 mm as shown in FIG.
A glass column type container (1) having a φ and a height of 200 mm was mixed and filled with 50 g of trimethylindium (TMI) and 50 g of stainless steel helipack. Next, the container (1) was immersed in a constant temperature bath at 25 ° C., and the carrier gas outlet (4) was connected to a liquid nitrogen trap for collecting TMI. The pipe connecting the outlet (4) and the liquid nitrogen trap was heated to 35 ° C. to prevent TMI from precipitating in this pipe. Then, 500 cc of hydrogen gas was flowed from the carrier gas inlet (3) of the container per minute, and the weight of the TMI collected in the liquid nitrogen trap was measured every 8 hours.

The results are shown in FIG. The vertical axis of the graph shown in FIG. 4 represents the TMI supply amount per hour, and the horizontal axis represents the usage rate of the supplied TMI in% by weight. T than this
The MI supply rate was stable until the usage rate was 70% by weight.

(Example 2) Two column-type containers filled with 50 g of TMI in Example 1 were connected in series as shown in FIG. 3 (a). Then, a hydrogen carrier gas was supplied to this apparatus in the same manner as in Example 1, and the TMI trapped in the liquid nitrogen trap was supplied.
Was measured. Similar experiments were performed three times to check reproducibility.

The results are shown in FIG. It can be seen from FIG. 5 that the feed rate of TMI was stable up to the usage rates of 70, 72, and 72% by weight in three experiments, and reproducibility was obtained regardless of the filling amount.

(Comparative Example 1) A conventional container as shown in FIG. 1 was filled with 50 g of TMI and 50 g of stainless steel helipack. Then, a hydrogen carrier gas was supplied to this conventional apparatus in the same manner as in Example 1 to measure the weight of the TMI collected in the liquid nitrogen trap.

The results are shown in FIG. From FIG. 6, the feeding rate of TMI was stable up to the usage rate of 60% by weight.

(Comparative Example 2) In a conventional container as shown in FIG.
MI 100 g and stainless steel helipack 100 g were mixed and filled. Then, a hydrogen carrier gas was supplied to this conventional apparatus in the same manner as in Example 1 to measure the weight of the TMI collected in the liquid nitrogen trap. Similar experiments were performed three times to check reproducibility.

The results are shown in FIG. From this, the feed rate of TMI was 47, 52, 55% by weight in three experiments.
Was stable until. It can be seen that the reproducibility is poor as compared with Example 2. Further, compared to the case where 50 g of TMI is filled in Comparative Example 1, the amount of filling can be increased to stably supply TM.
The proportion of I is decreasing.

[0018]

[Effect of the Invention] When a solid organometallic compound and its carrier or packing are uniformly filled in a filling container, a column type container is used, and the carrier gas outlet tube inside the conventional container is removed to improve reproducibility. It became possible to supply a solid organometallic compound to a vapor phase growth apparatus. Further, by connecting such a column type container, the filling amount of the solid organometallic compound can be increased while keeping the filling state uniform, which is very effective in mass production using a vapor phase growth apparatus. Is.

[Brief description of drawings]

FIG. 1 is an explanatory diagram showing a conventional device.

FIG. 2 is an explanatory view showing an embodiment of the device of the present invention.

3A is an explanatory view showing another embodiment of the present invention, and FIG. 3B is an explanatory view showing still another embodiment of the present invention.

FIG. 4 is a chart showing the results of a solid organometallic compound supply test by the device of the present invention.

FIG. 5 is a chart showing the results of a solid organometallic compound supply test using another apparatus of the present invention.

FIG. 6 is a chart showing the results of a supply test of a solid organometallic compound by a conventional device.

FIG. 7 is a chart showing the results of a solid organometallic compound supply test using another conventional apparatus.

[Explanation of symbols]

 1,1 'container 2 tube 3 carrier gas inlet 4 carrier gas outlet 5 flow meter 6 filter

Claims (2)

[Claims] 1. A container is filled with an organometallic compound which is solid at room temperature, and a carrier gas is passed through the container,
In a solid organometallic compound supply device for obtaining a carrier gas mixed with an organometallic compound, the container shape is a column-shaped straight tube, the carrier gas inlet is provided at one of the upper and lower ends of the container, and the organic gas is provided at the other end. A solid metal-organic compound supply device in metal-organic vapor phase epitaxy, characterized in that a carrier gas outlet mixed with a metal compound is provided. 2. A solid organometallic compound supply device, wherein the column type straight pipes according to claim 1 are connected in parallel or in series.