JP3020668B2 - Metal halide gas generating method, film forming method, and film forming apparatus - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for generating a metal halide gas, a method for forming a film using the method for generating a metal halide gas, and a film forming apparatus directly used in the method.

[0002]

2. Description of the Related Art Conventionally, as an apparatus for forming a metal oxide film on an object to be formed, for example, a film forming apparatus as disclosed in Japanese Patent Application Laid-Open No. 59-98726 is known.

FIG. 5 shows such a film forming apparatus. Reference numeral 11 denotes a cylindrical water-cooled jacket which is a container for forming a film. This water-cooled jacket 1
1, that is, inside the reaction chamber 13, a cylindrical graphite inner case 15 for uniformizing the ambient temperature.
A heater 17 made of carbon for heating the reaction chamber 13 is provided between the graphite inner case 15 and the water cooling jacket 11. The graphite inner case 15 is formed by connecting a plurality of case pieces. Further, in the graphite inner case 15 of the reaction chamber 13, the object 1 on which a film is to be formed is formed.
9 are accommodated.

[0004] Above and below the water cooling jacket 11,
Lid members 21 and 23 for closing water cooling jacket 11
Is disposed, and the upper lid member 21 has, for example,
A gas introduction passage 25 for introducing a metal halide gas containing Si, C, etc. is formed.
A gas lead-out passage 27 for leading out unnecessary exhaust gas after the reaction has occurred is formed.

In the film forming apparatus configured as described above, the film-forming body 19 is accommodated in the water-cooled jacket 11 of the reaction chamber 13, and the inside of the reaction chamber 13 is heated to a predetermined temperature by the heater 17. In order to deposit the film, a metal halide gas containing each component is introduced into the reaction chamber 13 from the introduction path 25 by a carrier gas such as Ar or H ₂ , and the introduced amount, flow rate, deposition temperature, furnace By controlling the internal pressure and the like, a desired film can be formed on the film-forming body 19.

When a desired film is formed on the film-forming body 19 using the film forming apparatus, a high-purity metal halide gas is used. Has been industrially mass-produced by reacting many times in a large-scale plant.

[0007]

However, there is a problem that the metal halide gas used in the above-mentioned conventional film forming apparatus is very expensive. In addition, there is a problem that it is difficult to form a desired film on the film-forming body 19 in some cases because there are few kinds of metal halide gases.

Further, in the conventional film forming apparatus, it is necessary to control the introduction amount, flow rate, deposition temperature, furnace pressure, etc. of the metal halide gas, but this requires an expensive control unit and sufficient steam. There is a problem that a partial heating means for obtaining the pressure is required, and the apparatus itself is increased in size and cost is increased.

The present invention provides a method for producing a metal halide gas which can easily and inexpensively obtain a desired metal halide gas, and uses this method to produce a metal oxide gas at a low cost and easily. It is an object to provide a film forming method and a film forming apparatus capable of forming a film.

[0010]

According to the method for producing a metal halide gas of the present invention, a halogen-containing gas (metal is contained) is contained in a reaction chamber containing an evaporation source composed of a metal oxide containing Zr and carbon. (Not included)) and heating the evaporation source to 1150 to 1400 ° C. to react the halogen-containing gas with the evaporation source to generate a metal halide gas.

Further, according to the film forming method of the present invention, a halogen-containing gas (not containing a metal) is supplied to an evaporation source composed of a metal oxide containing Zr and carbon, and the evaporation source is heated to 1150 to 1400 ° C. Heating is performed to cause the halogen-containing gas to react with the evaporation source to generate a metal halide gas. The metal halide gas is supplied to a surface of a film to be formed in a reaction chamber, and at the same time, an oxygen-containing gas is formed into the film. This is a method in which the metal halide gas and oxygen react with each other to supply metal to the body surface to generate a metal oxide, and the metal oxide is deposited on the surface of the film-forming target. In this case,
It is desirable that the evaporation source and the film-forming object be installed in the same reaction chamber.

Further, in the film forming apparatus of the present invention, a reaction chamber in which the inside is maintained under reduced pressure, and carbon contained in a metal oxide containing Zr, which is housed in a predetermined position in the reaction chamber, is added. An evaporation source heated to 1150 to 1400 ° C., an introduction path for introducing a halogen-containing gas (not including a metal) into the evaporation source in the reaction chamber, and housed in the reaction chamber downstream of the evaporation source. And an oxygen supply path for supplying an oxygen-containing gas to the surface of the film-formed body.

[0013]

According to the method for producing a metal halide gas of the present invention, a metal oxide and a halogen-containing gas are simply used in a single reaction chamber without using a special apparatus to convert a desired metal halide gas. It is inexpensive and can be easily obtained. Further, by reacting the thus obtained metal halide gas with oxygen on the surface of the film-forming object, a metal oxide film can be easily formed on the surface of the film-forming object at low cost.

Further, since the formation of the metal halide gas and the metal oxide film can be carried out in a reaction system in which only the temperature conditions are different, controlling the temperature conditions allows the generation of the metal oxide film to be reduced from the generation of the raw material. Up to film formation can be performed in a single reaction chamber. Thereby, a high-purity metal halide gas and an oxide powder can be used as main raw materials, the apparatus can be reduced in size, the desired metal halide gas and metal oxide film can be manufactured at low cost, and Can be easily obtained.

[0015]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, a film forming apparatus according to the present invention will be described in detail with reference to the drawings. 1 and 2 show an embodiment of the film forming apparatus of the present invention, and reference numeral 31 indicates a reaction chamber for forming a film. The reaction chamber 31 is constituted by a highly airtight cylindrical body 33 which is excellent in airtightness itself and sufficiently durable against heating. For example, alumina or mullite which is chemically stable and excellent in heat conductivity is used. And the like are preferable, and it is desired that the ceramic be a highly dense body having a relative density of 95% or more.

A cylindrical graphite tube 35 for equalizing the ambient temperature is accommodated in the highly airtight cylindrical body 33, that is, in the reaction chamber 31, and the graphite tube 35 has a cylindrical graphite tube 35 therein. , Four long film-formed bodies 37 having a bottomed circular tube are accommodated. These film formation bodies 37 are made of, for example, porous Ni having gas permeability.
It is formed by -ZrO _2.

An upper water-cooling jacket 39 is disposed above the highly airtight cylinder 33, and is an introduction passage for introducing a gas such as HCl as a halogen-containing gas or Ar as a carrier gas into the reaction chamber 31. 41 is inserted through the upper water cooling jacket 39, and one end of the introduction path 41 is connected to the gas control device 43. With this gas control device 43,
The introduction amount, flow rate, and the like of a gas such as HCl or Ar are adjusted, and introduced into the reaction chamber 31 via the introduction path 41.

A lower water-cooling jacket 45 is disposed below the highly airtight cylinder 33, and a lead-out path 47 for leading exhaust gas to the outside is inserted through the lower water-cooling jacket 45. One end of 47 is connected to an exhaust unit 49.

A heater 51 is provided around the highly airtight cylinder 33, and around the heater 51, as shown in FIG.
As shown in FIG. 2, two heat insulating members 55 having a semicircular cross section connected on one side by a hinge 53 are arranged.
5 is openable and closable as shown in FIG.

As shown in FIG. 1, the heater 51 is composed of heater members 57, 59, 61, 63, 65 divided into five in the axial direction of the highly airtight cylindrical body 33. , These heater bodies 57, 59, 61, 63, 6
5 is also divided into ten heating elements 67 in the circumferential direction of the highly airtight cylindrical body 33 as shown in FIG. These heating elements 67 are made of, for example, ZrSi ₂ and are attached to the inner surface of the heat insulating member 55.

The heater bodies 57, 59, 61, 63, 65
Are connected to the heater control device 69 as shown in FIG. 1, respectively, and the heater members 57, 59, 61, 6 at predetermined positions according to the length of the film-forming body 37 arranged in the reaction chamber 31.
For example, in the case of FIG.
9, 61 will be activated.

Further, in the graphite tube 35,
An evaporation source 71 composed of a metal oxide and carbon for depositing a film having a desired composition, for example, a metal oxide composed of stabilized ZrO ₂ in which 8 mol% of Y ₂ O ₃ is dissolved, is added to ZrO ₂ . An evaporation source 71 prepared by adding carbon to such an extent that oxygen can be sufficiently trapped is disposed above the film formation target 37. That is, as shown in FIG. 4, the graphite tube 35 is vertically divided into two parts, a lower part of the upper tube 73 is screwed with a porous raw material support member 75, and an upper part thereof houses the evaporation source 71. I have. An oxygen supply path 77 is inserted from below into the film formation target 37. The oxygen supply path 77 is connected to a bubbling device 79 for generating a mixed gas of H ₂ O (steam) and H _2. It is connected.
The bubbling device 79 introduces H ₂ into water (H ₂ O) and generates H ₂ O and H ₂ as steam.

As an example of forming a metal oxide film on the film-forming body 37 by using the film forming apparatus configured as described above, ZrO _{2 in} which Y ₂ O ₃ is dissolved at a rate of 8 mol% is used. A method for forming a film will be described. A reaction chamber 3 in which a film forming body 37 which is a predetermined substrate on which a film is formed is kept at a furnace pressure of 20 torr.
1 and the heater 51 heats the inside of the reaction chamber 31 to a predetermined temperature (for example, 1250 ° C. for the evaporation source 71 and 1150 ° C. in the vicinity of the film-forming body 37) while introducing HC
1 gas at a flow rate of 200 sccm, and Ar gas as a carrier gas at a flow rate of 5000 sccm.
This is performed by discharging unnecessary exhaust gas introduced into the inside 1 from the outlet 47.

That is, the HCl gas introduced from the introduction passage 41 reacts with the evaporation source 71 in the reaction chamber 31, and YCl ₃ and Z
A metal halide gas of rCl ₄ is generated. The generated gas is supplied to the surface of the film-forming body 37 and
An oxygen-containing gas consisting of H ₂ O and H ₂ is supplied from the opposite side at a flow rate of 600 sccm, and the metal halide gas reacts with H ₂ and O ₂ that have passed through the film formation body 37, thereby forming a film. 8 mol% of Y ₂ O ₃
Is formed into a ZrO ₂ metal oxide film.

The above-mentioned reaction system will be described in detail.

Reacts with source 71,

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[0027]

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The above reaction occurs to generate a metal halide gas and the like. According to this reaction, the CO ₂ gas and the H ₂ O gas generated simultaneously with the metal halide gas are decomposed in the furnace, and the CO gas, the O ₂ gas, and the H ₂ gas may be generated.

Next, the H ₂ and O ₂ gases that have passed through the film forming body 37 are

Note

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[0031]

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As described above, a dense 8 mol% Y ₂ O ₃ -ZrO ₂ metal oxide solid solution film is formed on the surface of the film formation target 37. The oxygen partial pressure of O ₂ transmitted through the film formation target 37, that is, the oxygen partial pressure in the vicinity of the film formation target 37 is 10 ^−10.
At less than atm%, no oxide film is formed and 10 ^-10 a
At tm% or more, the oxide film starts to be formed.

In the above-described method for generating a metal halide gas, a halogen-containing gas is introduced into the reaction chamber 31 containing an evaporation source 71 made of metal oxide and carbon, and the evaporation source 71 is kept at a predetermined level. By heating to a temperature and reacting the halogen-containing gas with the evaporation source 71, a desired metal halide gas can be easily obtained at low cost. By reacting the metal halide gas thus obtained with oxygen on the surface of the film-forming body 37,
A metal oxide film can be easily and inexpensively formed on the surface of the film formation target 37. Further, a reaction chamber 31 whose inside is maintained under reduced pressure, and an evaporation source 7 accommodated in a predetermined position in the reaction chamber 31 and formed by adding carbon to a metal oxide.
1, an introduction path 41 for introducing a halogen-containing gas into an evaporation source 71 in the reaction chamber 31, a film-forming body 37 accommodated in the reaction chamber 31 downstream of the evaporation source 71, and a film-forming body 37
And an oxygen supply path 77 for supplying an oxygen-containing gas to the surface of the metal oxide film. By controlling the temperature conditions in the formation of the metal halide gas and the metal oxide film, The film formation can be performed in the single reaction chamber 31, the device can be reduced in size, and a desired metal oxide film can be easily obtained at low cost.

[0034] In the above embodiment has described the example that generated the solid solution film of dense Y ₂ O ₃ -ZrO ₂ on the surface of the HiNarumakutai 37, the film formation apparatus of the present invention to the above examples The present invention is not limited thereto, and may be used, for example, when forming an Al ₂ O ₃ film.

In the above embodiment, the highly airtight cylinder 3
Although an example in which 3 is formed of alumina or mullite has been described, the film forming apparatus of the present invention is not limited to the above-described embodiment. Other known ceramics may be used.

Further, in the above embodiment, an example was described in which Cl ₂ gas as a halogen-containing gas was introduced from the introduction path 41. However, the film forming apparatus of the present invention is not limited to the above embodiment. , HCl, the same result is obtained.

The flow rate of the halogen-containing gas is 2 to 20.
0 sccm, the temperature of the evaporation source 71 is 1150 to 1400
The temperature of the film formation target 37 is preferably 1000 to 1200 ° C., and the pressure in the reaction chamber 31 may be a reduced pressure, and is preferably 200 torr or less.

[0038]

As described above, according to the method for producing a metal halide gas of the present invention, a desired metal halide gas can be produced at a low cost by using a metal oxide and a halogen-containing gas in a single reaction chamber. And it can be obtained easily. Further, by reacting the thus obtained metal halide gas with oxygen on the surface of the film-forming object, a metal oxide film can be easily formed on the surface of the film-forming object at low cost. Further, the generation of the metal halide gas and the generation of the metal oxide film on the surface of the film-forming object can be performed in a single reaction chamber. The material film can be easily obtained at low cost.

[Brief description of the drawings]

FIG. 1 is an explanatory view showing a film forming apparatus of the present invention and the vicinity thereof.

FIG. 2 is a cross-sectional view taken along line AA of FIG.

FIG. 3 is a plan view showing a state where the heat insulating member of FIG. 2 is opened.

FIG. 4 is an explanatory diagram for explaining a reaction in a reaction chamber of FIG. 1;

FIG. 5 is a longitudinal sectional view showing a conventional film forming apparatus.

[Explanation of symbols]

 31 Reaction Chamber 33 Highly Airtight Cylindrical Body 37 Film Deposition Body 41 Introduction Path 71 Evaporation Source 77 Oxygen Supply Path

Claims (4)

(57) [Claims] 1. A halogen-containing gas (containing no metal) is introduced into a reaction chamber containing an evaporation source composed of a metal oxide containing Zr and carbon, and the evaporation source is heated to 1150 to 1400 ° C. A method for producing a metal halide gas, comprising heating and reacting the halogen-containing gas with the evaporation source to produce a metal halide gas. 2. A halogen-containing gas (containing no metal) is supplied to an evaporation source comprising a metal oxide and carbon containing Zr, and the evaporation source is heated to 1150 to 1400 ° C. By reacting with the evaporation source to generate a metal halide gas, by supplying the metal halide gas to the surface of the film-forming body in the reaction chamber and simultaneously supplying an oxygen-containing gas to the surface of the film-forming body, A film forming method, wherein a metal oxide is generated by reacting the metal halide gas and oxygen, and a metal oxide film is deposited on a surface of the film formation target. 3. The film forming method according to claim 2, wherein the evaporation source and the object are placed in the same reaction chamber. 4. A reaction chamber in which the inside is maintained under reduced pressure, and carbon is added to a metal oxide containing Zr, which is housed at a predetermined position in the reaction chamber and contains 1150 to 14
An evaporation source heated to 00 ° C., an introduction path for introducing a halogen-containing gas (not containing a metal) into the evaporation source in the reaction chamber, and a substrate accommodated in the reaction chamber downstream of the evaporation source. A film forming apparatus comprising: a film body; and an oxygen supply path for supplying an oxygen-containing gas to the surface of the film-formed body.