JPS63162036A - Production of solid simple substance - Google Patents

Abstract

PURPOSE:To accelerate the liq. phase growth of the titled substance on a surface of a base substance, by heating the base substance in the condition that a part of the base substance is dipped in a liq. contg. an inorganic compd., decomposing the inorganic compd. and allowing the simple substance of the aimed element to deposit on the surface of the base substance. CONSTITUTION:A liq. of raw material 7 discharged from a liq. outlet 3 is introduced into a reaction container 1 from a liq. inlet 2 and circulated with a circulating device. The raw liq. 7 is kept 70-80 deg.C and is suitably supplied with the operation of reaction. Next, the inside of the reaction container 1 is kept in Ar atmosphere by introducing Ar from the gas inlet 4 into the reaction container 1 and allowing it to flow out from the gas outlet 5. Thereafter the base substance 8 is indirectly heated to 1,500-1,600 deg.C by heating a heater with an electric source 10. Boron is deposited on the surface of the base substance 8 by keeping the above-mentioned condition.

Description

[Detailed Description of the Invention] [Object of the Invention] (Industrial Field of Application) The present invention relates to a method for manufacturing a solid element, and more specifically to a method for easily and rapidly growing a solid element on the surface of various substrates in a liquid phase. Related.

(Prior Art) Conventionally, various methods have been proposed and put into practical use as methods for producing solid elements. Generally, there are several manufacturing methods for one type of solid element, and among these manufacturing methods, there are some that are commonly applied to the production of several solid elements.

Below, some methods for producing solid elements will be exemplified.

Arsenic As (sublimation point 615℃) is arsenic trioxide AS203
It is produced by reducing with carbon C.

Boron B (melting point 2225°C) is boron tribromide BBr3
It is produced by pyrolyzing a gas over a heated metal gas.

Aluminum Affi (11 points 660℃) is alumina Affi203 with cryolite 3NaF-A (lFa (1)
It is produced by dissolving a molten salt in an electrolytic bath, electrolyzing it using carbon as an electrode, causing a reaction of 2A + 3C → 4Aff + 3CO2, and depositing AQ on the cathode.

Molybdenum (melting point 2615℃) is molybdenum oxide MO
It is produced in powder form by reducing O3 with hydrogen at around 1000°C.

Titanium (melting point 1668° C.) is produced by reducing titanium tetrachloride T i CI2+ with magnesium using the Kroll method.

However, these methods require large-scale equipment or
There are problems such as slow production speed and low yield. Also,
There are problems in that the purity is poor and purification is often difficult because by-products get mixed into the solid substance, and because the manufacturing conditions are generally harsh, components of manufacturing equipment components get mixed into the solid substance.

(Problems to be Solved by the Invention) The present invention has been made to solve the above-mentioned problems, and its purpose is to provide a method for easily and quickly producing a pure solid element. .

[Structure of the Invention] (Means for Solving the Problems) The method for producing a solid simple substance of the present invention involves the step of immersing at least a portion of a substrate in a liquid containing an inorganic compound of a target element as a raw material. The method is characterized in that the substrate is heated to decompose the inorganic compound, and a solid element of the target element is precipitated on the substrate.

In carrying out the method of the present invention, first, a substrate is placed in a reaction vessel. As the material of the substrate, various single materials, compounds, alloys, or composite materials can be used, and although not particularly limited, it is preferable to use a conductive material such as WlSi or graphite that can be heated with electricity. Furthermore, it is more desirable to use the same material as the solid substance to be subjected to liquid phase growth as the substrate. This is because the growing solid element is less likely to be contaminated by the substrate. The shape of the substrate is also not particularly limited, and linear, plate-shaped, etc. are used.

Next, a liquid containing an inorganic compound serving as a raw material is placed in the reaction container, and at least a portion of the substrate is immersed therein.

Examples of the above-mentioned liquids include ■Those consisting only of liquid inorganic compounds;■Those in which, in addition to liquid inorganic compounds, components such as argon and nitrogen that do not adversely affect the liquid phase growth of a solid substance coexist. I can do it. The inorganic compound does not necessarily have to be a liquid when wet, but only needs to become a liquid when cooled or heated. Note that when such an inorganic compound is thermally decomposed, a solid element and a living organism are generated. For this reason, it is desirable to use an inorganic compound whose by-product becomes a gas at the manufacturing temperature so that the by-product is not mixed into the solid substance. Specifically, the inorganic compound is ASH3(-1
Liquid at 17-155℃), BBr3 (-46-91℃
liquid>, Ga2H6 (liquid at -21 to 130℃), M
o CrS (liquid at 194-268°C), Pb
(CH3)4 (-27, liquid at 5-110℃),
TiCl2 (liquid at -25 to 136 °C), WCβs
(liquid at 275-347°C).

The liquid of such an inorganic compound may be left standing in the reaction container or may be allowed to flow.

When flowing liquid, the method may be a circulation method,
It may be non-@cyclic.

Next, the substrate is heated. The appropriate heating temperature for the substrate is not particularly limited, since it also depends on conditions such as the type of inorganic compound, the flow rate of the liquid, and the material of the substrate. However, the temperature needs to be higher than the decomposition temperature of the inorganic compound (at the decomposition temperature, the inorganic compound may be a gas) and lower than the melting point or sublimation point of the solid temperature. To give a specific example, for example, A
When depositing S (sublimation point 615°C), the substrate is
Heat to ~615°C. In addition, BBr3 (decomposition temperature 13
When precipitating B (melting point: 2225°C) using B (melting point: 2225°C) as a raw material, the substrate is heated to 1300 to 2225°C. In addition, when precipitating MO (2615°C per point) using MOC/2s (decomposition temperature 1300°C) as a raw material, the substrate is
Heat to 300-2615°C. When the substrate is heated in this manner, the inorganic compound is thermally decomposed, and a solid element of the target element is precipitated on the surface of the substrate.

The atmosphere of the entire reaction system mentioned above may be air, but
An atmosphere of an inert gas such as Ar or N2 is preferable because the inorganic compound is more stable and side reactions are suppressed.

In addition, in the above explanation, ■ installation of the substrate, ■ introduction of liquid,
Although the case has been described in which the operations are performed in the order of (1) heating the substrate, the order is not limited to this, and for example, the order of (1) and (2) may be reversed.

(Operation) According to the method of the present invention as described above, the inorganic compound in the raw material liquid is excited and decomposed, and a solid ψ body grows on the surface of the substrate in a liquid phase. At this time, since the raw material is a liquid, the frequency of excitation and decomposition increases, resulting in rapid growth of a solid substance. Furthermore, in principle, side reactions are unlikely to occur, and by-products can be easily removed, so reverse reactions are suppressed and yields are increased. In addition, the raw material liquid can be easily purified by distillation, etc., solid impurities remain in the liquid, and the manufacturing conditions are mild and it is possible to prevent the components of the manufacturing equipment from mixing with the solid itself. The purity of the single substance increases. Furthermore, a simple manufacturing device is sufficient.

(Example) Embodiments of the present invention will be described below with reference to the drawings.

Example 1 FIG. 1 is a schematic diagram of a reaction apparatus used in Example 1. In FIG. 1, a reaction vessel 1 is provided with a liquid population 2 and a liquid outlet 3 on its bottom surface, and a gas population 4 and a gas outlet 5 on its top surface. Further, a cylindrical substrate holder 6 is provided in the center of the reaction container 1 . A raw material liquid 7 is accommodated inside this reaction vessel 1 . A substrate 8 is placed in the substrate holder 6 of the reaction vessel 1, and its lower surface is immersed in the raw material liquid 7. Further, a heater 9 is provided adjacent to the base 8, and this heater 9 is connected to a power source 10.

Using the above reaction Vi, boron B was precipitated as follows. First, the base body 8 has a diameter of 20 m and a thickness of 2 m.
A positive alumina disk was prepared and placed in an alumina substrate holder 6 having a diameter of 20H.

Next, the liquid outlet 3 is closed, and the raw material liquid 6, BBr3 (liquid at -46 to 91°C) is transferred from the liquid population 2 to the reaction vessel 1.
When the lower surface of the substrate 8 was sufficiently immersed in the raw material liquid 7, the liquid outlet 3 was opened. Thereafter, the raw material liquid 7 discharged from the liquid outlet 3 is processed by a circulation device (not shown).
was circulated so that it was introduced into the reaction vessel 1 from the liquid population 2. Note that the temperature of the raw material liquid 7 was maintained at 70 to 80'C.

Further, during the reaction operation described later, the consumed raw material liquid 7 was replenished as appropriate. Subsequently, Ar was introduced into the reaction vessel 1 through the gas port 4 and flowed out from the gas outlet 5 to maintain an Ar atmosphere inside the reaction vessel 1.

Next, power was supplied from the power supply 10 to heat the heater, and the base 8 was indirectly heated to 1500 to 1600°C. When this state was maintained, boron B was deposited on the surface of the substrate 8. In addition, D1 forms bromine Br2 (gaseous at 59°C or higher)
was released from the gas outlet 5 to the outside of the system.

By the above method, a boron layer having an average thickness of 2 mm was formed on the surface of the substrate 8 in one hour of precipitation. The purity of this boron layer was 99.8%. Further, the yield was calculated from the weight loss of BBrs and the amount of the porium layer produced, and was found to be 94%.

Example 2 FIG. 2 is a schematic diagram of a reaction apparatus used in Example 2. In FIG. 2, a reaction vessel 11 is provided with a gas port 12 and a gas outlet 13 on its upper surface. A raw material liquid 14 is stored in advance in this reaction vessel 11, and left as it is during a precipitation operation to be described later. This raw material liquid 1
A substrate 15 is immersed in the substrate 4, supported at both ends by electrodes 16.16. A power source 17 is connected between the electric bridges 16, 16.

Using the above reaction apparatus, molybdenum MO was prepared as follows.
was manufactured. First, the raw material liquid 14 is placed in the reaction vessel 11 in advance.
MOCffis (liquid at 194-268°C) was introduced and maintained at 200-220°C. Next, a molybdenum wire having a diameter of 0.2 M and a length of 40 mm was immersed in the raw material liquid 14 as the base 15, and both ends of the wire were supported by molybdenum electrodes 16 and 16. Subsequently, Ar was introduced into the reaction vessel 11 through the gas inlet 12 and flowed out through the gas outlet 13 to maintain an Ar atmosphere inside the reaction vessel 11. Next, the base body 15 is directly heated with electricity by the Ti source 17 to 180
The temperature was maintained at 0-1900°C. As a result, a layer of molybdenum was deposited on the surface of the substrate 15. In addition, by-produced bromine Cf
;12 (gaseous at temperatures above -34°C) was discharged from the gas outlet 13 to the outside of the system.

By the above method, a layer of molybdenum having an average thickness of 1 was formed on the surface of the substrate 15 in a one hour precipitation operation.

The purity of this molybdenum layer was 99.99%. Moreover, when the yield was calculated, it was 96%.

[Effects of the Invention] As detailed above, according to the method of the present invention, a highly pure solid element can be produced easily and quickly with a high yield, and other industrially significant effects are achieved.

[Brief explanation of the drawing]

Figure 1 is a schematic configuration diagram of a reaction apparatus for liquid phase growth of a solid element used in Example 1 of the present invention, and Figure 2 is a schematic diagram of a reaction apparatus for liquid phase growth of a solid element used in Example 2 of the present invention. 1 is a schematic configuration diagram of a reaction apparatus for producing 1... Reaction vessel, 2... Liquid inlet, 3... Liquid outlet, 4... Gas inlet, 5... Gas outlet, 6...!
! Body holder, 7... Raw material liquid, 8... Substrate, 9...
・Heater, 10... Power supply, 11... Reaction container, 12
... Gas inlet, 13... Gas outlet, 14... Raw material liquid, 15... Substrate, 16... Electrode, 17... = 1
? I! .

Claims (1)

[Claims] heating the substrate while at least a portion of the substrate is immersed in a liquid containing an inorganic compound of the target element as a raw material;
A method for producing a solid element, which comprises decomposing the inorganic compound and depositing a solid element of the target element on the substrate.