JPS604123B2 - Method and apparatus for producing new hydrogen-containing silicon material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method and apparatus for producing a novel hydrogen-containing silicon material.

Regarding a new hydrogen-containing silicon material that is composed of a four-coordinated Si lattice and a surrounding Si ratio or/and Sj & shell and contains hydrogen in the Si lattice, see Samurai Sho 56-7020.
It is described in the specification of No. 0 (see Japanese Unexamined Patent Publication No. 57-205312).

In principle, this hydrogen-containing silicon material can be generated on a substrate by sputtering by applying a voltage between a silicon target and the substrate placed facing each other in a hydrogen atmosphere. Sputtering is carried out in a single sputtering chamber in a batch manner, and a method and apparatus suitable for producing a target product in large quantities on an industrial scale have not yet been developed. The present inventors completed the present invention as a result of various studies aimed at obtaining a method and apparatus capable of continuously producing the hydrogen-containing silicon material on an industrial scale. It is therefore an object of the present invention to provide a method and apparatus capable of mass producing new hydrogen-containing silicon materials.

The method for producing a new hydrogen-containing silicon material according to the present invention has a particle size of 3
A slurry in which silicon powder with a size of 0.00 mesh or less is dispersed in a liquid silicon-containing compound is made into fine particles using SiH2 gas or SiH4 gas, and then ejected into hydrogen plasma. and S
This is because iH3 fine particles are generated and hydrogen is introduced into the Si-Si network.

The apparatus according to the present invention also includes a reaction chamber, a plasma torch provided at the center of one end of the reaction chamber, a plurality of silicon powder slurry mist nozzles arranged around the plasma torch, and a plurality of silicon powder slurry mist nozzles arranged in front of the plasma torch. It consists of a cylindrical magnet for plasma absorption and a cooled product collection wall provided at the other end of the reaction chamber. The method and apparatus for producing a novel hydrogen-containing silicon material according to the present invention will be explained below with reference to FIG.

First, the SUS butterfly valve 2 of the stainless steel reaction chamber 1 is opened and connected to the exhaust to create a vacuum of about 10-6 tons in the reaction chamber. For example, the reaction chamber can be brought to a vacuum of 10-3 Tom using an oil rotary pump, and then brought to a vacuum of 10-6 Ton using a diffusion pump using oil, mercury, or the like. The exhaust system is equipped with a liquid nitrogen trap. Next, the argon gas and hydrogen gas measured by the regulator and flow meter from the argon gas cylinder 3 and the hydrogen gas cylinder 4 are passed through the manhold into the Ar gas cylinder.
/Hiroshi=8/2 to 2 to 8 to form a plasma gas, which is supplied to the reaction chamber at a constant flow rate via the plasma torch 5. At this time, when the (power source) is connected to the plasma torch (AMH2) and plasma is generated, hydrogen gas is dissociated and ionized according to the 21st and 10th e of the day, and the desired reaction takes place. By providing the cylindrical magnet 6 to surround the plasma formed in the reaction chamber from the tip of the plasma torch, the length of the plasma can be increased to 10 skins or more. Note that it is preferable to cool the portion of the plasma torch outside the reaction chamber with water to prevent overheating. Reaction chamber 1
For example, the inner wall is 27 meters long, 50 meters long, and the inner wall is polished to a #40 false surface. Both lids are similarly made of stainless steel, and both are sealed with O-rings. On the other hand, an appropriate amount of slurry (solid content 10 to 4% by weight) in which silicon powder having a particle size of 300 mesh is dispersed in a silicon-containing liquid such as SIC14 is pumped into the double conduit 9 from the slurry tank 7. It is injected into the plasma via the tube/from the nozzle 10.

This injection is carried out by injecting a specific gas or/and SiH4 gas etc. from a cylinder 8 into a nozzle through the outer tube of the double conduit 9 at a pressure of 1 to 3 k9/mass G, and the slurry is is miniaturized and supplied into the plasma. Since plasma exists only in a very limited area, a nozzle as shown in FIGS. 2 and 3 is used to carry out the reaction between silicon powder and plasma hydrogen with good efficiency. Figure 2A is a side view showing the arrangement of the nozzles, and Figure 2B is a front view thereof.As is clear from these figures, six nozzles are arranged so as to surround the plasma torch. . The nozzle ports are arranged with a slope so that the & gas or the SiH4 gas injected from each nozzle is concentrated at one point C in the center of the plasma. In addition, in order to make the droplets of silicon powder slurry as small as possible, preferably in the form of an aerosol, the nozzle has a double structure as shown in FIG. Since the silicon slurry is atomized at the nozzle port through which the SiH2 gas or SiH4 gas passes, changes in the viscosity of the slurry and evaporation of the sooty liquid SIC14 during transportation can be prevented. The slurry is given a large rotational speed by the liquid flow rotary plate 103 at the nozzle outlet, so the slurry alone can be atomized, but the gas or SiH4 gas passing through the outer pipe of the double conduit 9 is used to reduce the slurry in the inner pipe on the way. After heat insulation, the slurry is rotated at the nozzle opening at an oblique angle of, for example, about 2 in the vertical direction and about 60 degrees in the horizontal direction, and is ejected into the reaction chamber at a speed close to the speed of sound to atomize the slurry. The aerosol-like liquid thus obtained dries instantaneously in the plasma and the surface of the silicon particle melts, so a liquid reaction takes place on the surface of the silicon particle and the surface of the silicon particle becomes SiH, SiH2, SiH
No. 3 (generally referred to as SiHx) is generated. Further, while passing through the plasma, the melting of the silicon particles gradually progresses from the surface to the inside, and the bond lattice structure of the silicon atoms becomes a liquid state, and the bonds between the silicon atoms become considerably relaxed. The plasma-formed particles thus enter the molten silicon and become trapped within its network structure. When the hydrogen-captured product passes through the cylindrical magnet, it collides with the collection wall 11 and is rapidly cooled. The collection wall rapidly cools the molten silicon to form -Si-Si
- Freezer 1 to collect the loose mesh structure
3, Freon gas is sprayed from the nozzle 12 onto the collecting wall to cool it to below -30°C. The pressure inside the reaction chamber during the reaction is adjusted by the butterfly valve 2 to 1 to 50 Tom. After a predetermined reaction time, when a sufficient amount of products has accumulated in the reaction chamber, the supply of slurry and propellant gas is stopped, then the plasma is extinguished, and nitrogen gas is introduced into the reaction chamber to reduce atmospheric pressure. After that, open the reaction chamber and collect the product.

Examples of the manufacturing method according to the present invention will be described below.

EXAMPLE A plasma gas having a mixing ratio of argon to hydrogen of 1:1 is supplied to a plasma torch at a flow rate of 3 mm/min.

The power for plasma generation at this time is the ship's armw (DC).

On the other hand, a mixed gas with a mixture ratio of hydrogen to SiH4 of 7:3 is supplied to the outer pipe of the double conduit 9 at a pressure of 1.5 k9/ that, and a slurry with a ratio of silicon powder (#300) to SIC14 of 1:1 is produced. (solid content 50%) is supplied to the inner tube of the double tube 9 at a flow rate of 0.12Z, and is injected from the L nozzle 10 toward the plasma to merge. In the plasma, a (Si-H) reaction was carried out while passing through a cylindrical magnet in a reaction chamber to obtain Si-Hx powder. The hydrogen content of this powder product was determined by gas chromatography to be 65 atom %.

[Brief explanation of the drawing]

FIG. 1 is a diagram for explaining the manufacturing apparatus of the present invention,
2A and 2B are a side view and a front view showing the layer arrangement of the spray nozzle, and FIG. 3 is a sectional view of the nozzle. Codes in the figure: 1...Reaction chamber, 2...Butterfly valve, 3...Argon gas cylinder, 4...
Hydrogen gas cylinder, 5...Plasma torch, 6.
...Cylindrical magnet, 7...Slurry tank, 8...
Cylinder, 9...Double conduit, 10, 12...
Nozzle, 11... Collection wall, 13... Freezer, 1
01... Slurry conduit, 102... Outer tube, 10
3...Liquid flow rotating plate. Figure 1 Figure 2 Figure 3

Claims (1)

[Claims] 1. A slurry in which silicon powder with a particle size of 300 mesh or less is dispersed in a liquid silicon-containing compound is heated with H_2 gas or Si
The silicon powder is made fine by H_4 gas and ejected into hydrogen plasma, and the silicon powder is reacted with the plasma-formed H and H^+ to generate SiH_2 and SiH_3 fine particles while introducing hydrogen into the Si-Si network. A method for producing a new hydrogen-containing silicon material. 2. A reaction chamber, a plasma torch provided at the center of one end of the reaction chamber, a plurality of silicon powder slurry spray nozzles arranged around the plasma torch, and a cylindrical magnet for plasma convergence arranged in front of the plasma torch. and a cooled product collection wall provided at the other end of the reaction chamber.