JP2012036027A - Reaction furnace for moisture generation - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a reaction furnace for moisture generation, which generates moisture with a high purity at a catalyst reaction temperature lower than ignition temperatures of a hydrogen gas and an oxygen gas without burning by supplying and catalytically reacting the hydrogen gas and the oxygen gas into a reaction furnace having a platinum catalyst layer, and which maintains the catalytic performance of the platinum catalyst layer for a long period of time and maintains the adherence to a barrier layer installed in between the platinum catalyst layer and a reaction-furnace base material.SOLUTION: The reaction furnace for moisture generation includes a reaction furnace body having a gas entrance and a moisture exit formed thereon, a barrier layer formed on the internal surface of the reaction furnace body, and a platinum catalyst layer formed on the barrier layer. The barrier layer contains YOwith a content of 90-99.5 wt.% and a metal oxide with a content of 0.5-10 wt.%, the metal oxide being other than YOand having -200 kJ/mol or lower of standard enthalpy change of formation per 1 mol of single bond between a metal atom and an oxygen atom.

Description

  In the present invention, hydrogen gas and oxygen gas are supplied into a reaction furnace having a platinum catalyst layer and subjected to a catalytic reaction, so that an ignition point (500 to 500 ° C.) of hydrogen gas and oxygen gas is obtained without burning (about 2000 ° C.). The present invention relates to a water generation reactor for generating high-purity water at a catalytic reaction temperature lower than 580 ° C. (400 ° C. or lower).

  2. Description of the Related Art Conventionally, there is known a water generation reactor used for continuously supplying ultrapure water in silicon oxide deposition using a water oxidation method in semiconductor manufacturing (for example, patents). Literature 1-5).

  For example, as shown in FIG. 4, a reactor main body having a reaction internal space P is formed by combining and welding the furnace main body members 22 and 23 in a facing manner. The reactor main body is provided with a raw material gas inlet 24, a moisture gas outlet 25, an inlet-side reflector 26, an outlet-side reflector 27, and the like, and the inner wall surface of the furnace body member 23 on the side facing the raw material gas inlet 24. Is formed by providing a platinum catalyst layer 28b.

  A barrier layer 28a is formed between the stainless steel base material of the reaction furnace and the platinum catalyst layer 28b, and the barrier layer prevents impurities in the base material from diffusing into the platinum catalyst layer 28b. Prevents layer degradation.

  The thickness of the barrier layer 28a is about 0.1 μm to 5 μm. For example, the barrier layer 28a made of TiN is formed by an ion plating method. Furthermore, the thickness of the platinum catalyst layer 28b is 1 nm to 0.5 mm, and is formed by, for example, a vacuum deposition method. In addition to the ion plating method, a PVD method such as an ion sputtering method or a vacuum vapor deposition method, a chemical vapor deposition method (CVD method), a hot press method, a thermal spray method, or the like can be used as a method for forming the barrier layer 28a. In addition to the vacuum deposition method, the platinum catalyst layer 28b is formed by ion plating, ion sputtering, chemical vapor deposition, hot pressing, or the like, and the barrier layer 28a is made of a conductive material such as TiN. For some materials, plating is also used.

International Publication No. 97/28085 Pamphlet JP 2000-169108 A JP 2000-169109 A JP 2000-169110 A JP 2002-274812 A

  However, the conventional barrier layer made of TiN or the like has a problem that the catalytic performance of the platinum catalyst layer is lowered when used for a long period of time. Moreover, there also existed a problem that the adhesive force (peeling strength) to a barrier layer fell by long-term use.

  The decrease in the catalyst performance of the platinum catalyst layer over time is considered to be one of the causes that impurities from the base material diffuse through the barrier layer in the platinum catalyst layer.

In addition, the time-dependent decrease in the adhesion force of the platinum catalyst layer to the barrier layer is caused by the oxygen (O ₂ radical) activated by the catalytic reaction passing through the platinum catalyst layer and gradually in the vicinity of the interface between the barrier layer and the platinum catalyst layer. This is considered to be because the adhesion between the barrier layer and the platinum catalyst layer is reduced by oxidizing it. Such a decrease in adhesion force is not enough to peel off the platinum catalyst under normal use conditions.For example, the platinum catalyst layer may be caused by an unexpected impact on the water generation reactor due to an unintended drop during maintenance. There is a risk of partial peeling. In addition, when the platinum catalyst layer is peeled off, the peeled platinum becomes a contamination, which has a serious adverse effect on the quality of the manufactured semiconductor. Further, when the platinum catalyst layer is peeled off, the peeled platinum has a small heat capacity, and the temperature rises due to the reaction heat generated by the catalytic reaction of hydrogen gas and oxygen gas, resulting in an ignition source. Safety issues also arise.

  Accordingly, the main object of the present invention is to provide a water generating reactor capable of maintaining the catalytic performance of the platinum catalyst layer and the adhesion of the platinum catalyst layer to the barrier layer for a long period of time.

As a result of diligent research, the present inventors have formed platinum from the base material of the reactor main body by forming a barrier layer made of a sintered body obtained by adding a predetermined amount of a certain metal oxide in Y ₂ O ₃ and firing it. It has been found that long-term catalytic performance can be maintained by preventing the diffusion of impurities into the catalyst layer for a long period of time, and that the platinum catalyst layer can maintain a high adhesion force with the barrier layer for a long period of time.

That is, the present invention has a reactor main body provided with a gas inlet and a moisture outlet, a barrier layer formed on the inner wall surface of the reactor main body, and a platinum catalyst layer formed on the barrier layer. and, the barrier _layer, Y ₂ and O 3 90 to 99.5 _wt%, the standard enthalpy of formation per single bond 1mol of Y 2 _{O 3} metal oxide other than the a and metal atoms and oxygen atoms -200kJ The present invention provides a moisture generating reactor containing 0.5 to 10% by weight of a metal oxide that is not more than / mol.

The metal oxide is preferably at least one selected from the group consisting of La ₂ O ₃ , CeO ₂ , Ce ₂ O ₃ , MgO, and ThO ₂ .

  The reactor main body is preferably formed of a material that does not have catalytic activity with respect to hydrogen and oxygen.

  It is preferable that at least one reflector is further provided in the reactor main body, and the reflector is formed of a material that does not have catalytic activity with respect to hydrogen and oxygen.

  The reflector is fixed to the reactor main body by a fixing screw via a spacer so that at least one of the gas inlet and the moisture outlet is shielded at a predetermined interval, and the spacer and the fixing screw are hydrogenated. In addition, it is preferably formed of a material having no catalytic activity with respect to oxygen.

  The material having no catalytic activity for forming the reflector is preferably an iron-chromium-aluminum alloy, an aluminum alloy, or a copper alloy.

  It is preferable that a portion having no platinum catalyst layer in the internal space of the reaction furnace body is covered with a non-catalytic layer made of a material having no catalytic activity with respect to hydrogen and oxygen.

  The moisture generating reactor further includes at least one reflector in the reactor body, and the reflector is covered with a non-catalytic layer made of a material having no catalytic activity with respect to hydrogen and oxygen. It is preferable.

  The reflector is fixed to the reactor main body by a fixing screw via a spacer so that at least one of the gas inlet and the moisture outlet is shielded at a predetermined interval, and the spacer and the fixing screw are hydrogenated. And a non-catalytic layer made of a material having no catalytic activity with respect to oxygen.

The non-catalytic layer made of the material having no catalytic activity is selected from the group consisting of TiN, TiC, TiCN, TiAlN, Al ₂ O ₃ , Cr ₂ O ₃ , SiO ₂ , CrN, and Y ₂ O _3. It is preferably formed of at least one material.

  The non-catalytic layer made of a material having no catalytic activity may be formed of the same material as the barrier layer.

The present _invention, Y ₂ O 3 _90~99.5 and _weight%, Y 2 _{O 3} standard enthalpy per single bond 1mol of a metal oxide metal atoms and oxygen atoms other than the following -200kJ / mol By using the barrier layer containing 0.5 to 10% by weight of the metal oxide, it is possible to suppress the deterioration of the barrier performance with time and the deterioration of the adhesive force with the platinum catalyst layer over time.

It is a graph which shows the evaluation test result of barrier performance. It is a graph which shows the test result which evaluated the adhesive force of a platinum catalyst layer and a barrier layer. It is a graph which shows the result of having tested the adhesive force to the TiN barrier layer of a platinum catalyst layer about a comparative example. It is a longitudinal cross-sectional view which shows one form of the conventional reactor for moisture generation.

  Hereinafter, an embodiment of a reactor for generating moisture according to the present invention will be described with reference to FIGS. In the present invention, the structure of the reactor for generating moisture is the same as that of the conventional one except that the material of the barrier layer 28a is mainly different, so refer to FIG.

In the moisture generating reactor, a barrier layer is formed on the inner wall surface of the outlet main body member 23, and a platinum catalyst layer 28b is formed on the barrier layer. Barrier layer of the present _invention, Y 2 _{O 3,} standard enthalpy ΔHf single bond 1mol per the metal atoms and oxygen atoms is less than -200kJ / mol _(other than Y 2 _{O 3)} and metal oxides, Is formed by a sintered body containing a ratio in a predetermined range.

Here, when the metal oxide other than Y ₂ O ₃ has a standard production enthalpy ΔHf per mol of a single bond between a metal atom and an oxygen atom exceeding −200 kJ / mol, the furnace body can be used for a long time. This is not preferable because the amount of impurities that diffuse from the main body 23 through the barrier layer and diffuse into the platinum catalyst layer 28b may increase and the barrier performance may deteriorate over time.

A metal oxide having a standard formation enthalpy ΔHf per mol of a single bond between a metal atom and an oxygen atom of −200 kJ / mol or less is, for example, Ta ₂ O ₅ , SiO ₂ , TiO ₂ , ZrO ₂ , Al ₂ O ₃ , HfO. ₂ , La ₂ O ₃ , CeO ₂ , Ce ₂ O ₃ , MgO, and ThO ₂ , and these metal oxides can be used alone or in combination. Among these metal _{oxides, La 2 O 3, CeO 2} , Ce 2 O 3, MgO, ThO 2 , the standard enthalpy of formation ΔHf of the single bonds 1mol per the metal and oxygen _atoms, the Y 2 _{O 3} Next, since it is a low value, it is preferable, and CeO ₂ or Ce ₂ O ₃ is particularly preferable because it can be sintered at about 400 ° C. by mixing with Y ₂ O ₃ .

The standard formation enthalpy ΔHf per mole of single bond between metal atom and oxygen atom in the metal oxide as described above is −205 kJ / mol for Ta—O bond, −228 kJ / mol for Si—O bond, and Ti—O bond. Is −228 kJ / mol, Zr—O bond is −275 kJ / mol, Al—O bond is −279 kJ / mol, Hf—O bond is −286 kJ / mol, La—O bond is −299 kJ / mol, and CeO ₂ is Ce. The —O bond is −272 kJ / mol, the Ce—O bond of Ce ₂ O ₃ is −299 kJ / mol, the Mg—O bond is −301 kJ / mol, and the Th—O bond is −306 kJ / mol. Incidentally, the Y—O bond of Y ₂ O ₃ is ΔHf = −318 kJ / mol.

The barrier layer of the present invention has 90 to 99.5% by weight of Y ₂ O ₃ , and a standard generation enthalpy ΔHf per mol of a single bond between a metal atom and an oxygen atom is −200 kJ / mol or less (other than Y ₂ O ₃ Metal oxide 1 having 0.5 to 10% by weight of metal oxide, preferably 95 to 99% by weight of Y ₂ O ₃ and the above ΔHf value (−200 kJ / mol or less, the same shall apply hereinafter). -5% by weight. When the total of Y ₂ O ₃ and the metal oxide having the ΔHf value is 100%, the content of the metal oxide having the ΔHf value is less than 0.5% by weight or exceeds 10% by weight. Since the barrier performance tends to deteriorate with time, it is not preferable. This is because a barrier layer composed of 90 to 99.5% by weight of Y ₂ O ₃ and 0.5 to 10% by weight of the metal oxide having the ΔHf value is a lattice defect in which the metal oxide having the ΔHf value is Y ₂ O ₃ . The content of the metal oxide having the ΔHf value exceeds 10% by weight when the total of Y ₂ O ₃ and the metal oxide having the ΔHf value is 100%. This is thought to increase the lattice defects of Y ₂ O ₃ .

  A barrier layer can be formed on the inner wall surface of the furnace body member 22 on the inlet side as well as the furnace body member 23 on the outlet side, and a platinum catalyst layer can be formed on the barrier layer. If the moisture generation reaction is actively performed in the vicinity of the inlet 24, the temperature of the inlet side connection fittings and the like may be excessively increased. Therefore, at least a radius of about 10 mm from the center of the raw material gas inlet 24 of the furnace body member 22 on the inlet side. It is desirable that the platinum catalyst layer not be formed in the range of 15 to 25 m.

For the base material of the reactor main body, for example, stainless steel such as SUS316L, nickel alloy steel, or nickel steel can be used. The platinum catalyst layer in the furnace is formed especially when the reaction furnace body is made of a material that can exert a catalytic activity on O ₂ and H ₂ such as stainless steel, nickel alloy steel, and nickel steel. It is desirable to form a non-catalytic layer having no catalytic activity against oxygen and hydrogen as a coating for preventing catalytic activity due to the base material. Examples of such a non-catalytic layer material include TiN, TiC, TiCN, TiAlN, Al ₂ O ₃ , Cr ₂ O ₃ , SiO ₂ , CrN, and Y ₂ O _3. The same material as the barrier layer can also be used. Two or more of these materials may be used.

The same applies to the reflectors 26 and 27 when the reflectors 26 and 27 are provided in the reaction furnace main body. That is, when the base material of the reflectors 26 and 27 is a material that can exert a catalytic activity on O ₂ and H ₂ , the surfaces of the reflectors 26 and 27 do not have catalytic activity against oxygen and hydrogen. It is desirable to form a non-catalytic layer.

  In addition, when using the same material as the said barrier layer of this invention as a non-catalytic layer for preventing the catalyst activity by a base material, it is the same material as the barrier layer of this invention mentioned above on the whole inner surface of the furnace main body members 23 and 24. After forming the film made of the platinum catalyst layer 28b, the platinum catalyst layer 28b can be formed only on a desired portion on the film.

  The reflectors 26 and 27 can be disposed facing each other in the reaction furnace. Although the reflectors 26 and 27 are formed in a disk shape in the illustrated example, the reflectors 26 and 27 may be capable of increasing the efficiency of diffusing the mixed gas by collision with the mixed gas flowing into the internal space P of the reactor. The form is not limited. The reflector 26 on the inlet side is fixed to the furnace main body member 22 by a fixing screw 30 via a spacer 31 so as to block the source gas inlet 24 through a certain gap from the furnace main body member 22 on the inlet side. The outlet-side reflector 26 is also fixed to the furnace main body member 23 by a fixing screw 30 via a spacer 31 so as to block the source gas inlet 24 through a certain gap from the outlet-side furnace main body member 22. . The reflector can be fixed not only by screwing but also by other fixing means such as welding. In addition, although the example provided with a pair of reflector was shown in the example of illustration, only one reflector may be sufficient and the reflector 27 of the exit side preferably may be provided in that case.

The mixed gas of oxygen and hydrogen injected toward the reflector 26 through the source gas inlet 24 is diffused in the internal space P after colliding with the reflector 26, and the diffused mixed gas is spread over the entire surface of the platinum catalyst layer 28b. The catalyst is activated by substantially evenly colliding over the entire area, and moisture gas is generated by the reaction of H ₂ and O ₂ . The moisture gas formed in the internal space P is led out to the moisture gas outlet 25 through the gap L between the outlet-side reflector 27 and the outlet-side furnace body member 23.

As a base material of the reactor main body members 22 and 23 of the reaction furnace and a base material of the reflectors 26 and 27, a catalytic activity is exerted on O ₂ gas and H ₂ gas such as stainless steel, nickel alloy steel and nickel steel. Instead of the obtained material, a material that does not have a catalytic activity for O ₂ gas or H ₂ gas, for example, an iron-chromium-aluminum alloy, an aluminum alloy, or a copper alloy may be used.

When the base material of the reactor body members 22 and 23 of the reaction furnace is formed of a material having no catalytic activity such as the above-described iron-chromium-aluminum alloy, aluminum alloy, or copper alloy, the barrier layer in the internal space In a portion other than the portion provided with the above, it is desirable to perform an appropriate surface treatment for preventing the release of the internal gas and the internal metal composition material to the outer surface of the non-catalytic material. As the surface treatment, a non-catalytic layer having excellent corrosion resistance, reduction resistance and oxidation resistance can be formed. As such a non-catalytic layer, TiN, TiC, TiCN, TiAlN, Al ₂ O ₃ , Cr ₂ O ₃ , SiO ₂ , CrN, Y ₂ O ₃ can be used. You may use above, You may use the same material as this invention barrier layer. In this case as well, when the same material as the barrier layer of the present invention is used as the non-catalytic layer for the surface treatment, the barrier layer of the present invention is also formed in a desired portion other than the lower layer of the platinum catalyst layer, A barrier layer and a non-catalytic layer can be formed simultaneously. The reflectors 26 and 27 are preferably subjected to the same surface treatment as described above.

  The barrier layer of the present invention can be suitably formed, for example, by a sol-gel method. For example, an organic solvent solution of yttrium alkoxide and an organic solvent of cerium alkoxide are formed on a base material of a furnace body formed of stainless steel or the like. A mixed solution mixed with the solution at a required ratio is applied by spin coating, dip coating, spray coating or the like, and after the coating film is dried, it is baked at 400 to 600 ° C. for 1 to 5 hours in an oxygen atmosphere. Thus, a film can be formed.

TiN, TiC, TiCN, TiAlN, Al ₂ O ₃ , Cr ₂ O ₃ , SiO ₂ , CrN, or Y ₂ O ₃ is a PVD method such as an ion plating method, a sputtering method, a vacuum evaporation method, or a chemical vapor deposition method. It can be formed to a thickness of 0.1 to 5 μm using a method (CVD method), a hot press method, a thermal spraying method, or the like. Y ₂ O ₃ can also be formed by a sol-gel method in the same manner as the barrier layer.

  When the barrier layer is formed by a wet method such as the sol-gel method, a film having a film thickness of about 50 nm can be obtained by one application and baking, so that a desired film thickness (for example, Application and baking are repeated a plurality of times until the thickness reaches 100 nm and 300 nm.

  A thicker barrier layer is preferred to improve the barrier performance to prevent impurities in the stainless steel matrix from diffusing into the platinum catalyst layer, but this will increase costs due to increased coating and firing times. The film thickness of the barrier layer is preferably 300 nm or less.

  On the other hand, since yttrium is an expensive material, it is preferable to reduce the cost by reducing the thickness of the barrier layer. However, if the thickness of the barrier layer is too thin, there is a risk that the barrier performance may be deteriorated. Since it becomes difficult to control the thickness, the thickness of the barrier layer is usually set to 100 nm or more, but if it is 50 nm or more, its function can be exhibited.

  The barrier layer is preferably formed by a sol-gel method from the viewpoint of cost reduction of manufacturing equipment, but is not limited thereto, and is not limited to a thermal spray method, a PVD method, a vacuum deposition method, a sputtering method, an ion plating method, or the like. A film can also be formed. According to a dry method such as a thermal spraying method, the thickness of the barrier layer can be increased without repeating the same process as in the wet method, but even in the case of the dry method, if the material cost is taken into consideration The film thickness of the barrier layer is preferably 5 μm or less.

  The platinum catalyst layer formed on the barrier layer can be formed by vacuum deposition, ion plating, sputtering, chemical vapor deposition, hot pressing, or the like.

  The film thickness of the platinum catalyst layer is preferably 0.1 μm to 3 μm (100 nm to 3000 nm). That is, if the platinum catalyst layer is too thin, the platinum catalyst layer cannot sufficiently perform the function as the catalyst and the function as the protective film. Therefore, the platinum catalyst layer is preferably 0.1 μm (100 nm) or more. On the other hand, if the platinum catalyst layer is considered to have a function as a catalyst and a function as a protective film of the barrier layer as will be described later, it is preferable to increase the film thickness. The thickness is preferably 3 μm (3000 nm) or less, and more preferably 0.5 μm (500 nm) or less.

  The invention will be further clarified by the following examples, which are merely illustrative of the invention.

Example [Example 1]
First, a circular substrate (diameter 35 mm × thickness 3 mm) made of SUS316L was prepared. Y ₂ O ₃ coating material (produced by Kojundo Chemical Laboratory Co., Ltd. YYK01LB Y-03: brown liquid: oxide concentration of 3 wt%) 97.5 wt% and CeO ₂ coating material (manufactured by Kojundo Chemical Laboratory Co., Ltd. CEK01LB (Ce-03: yellow-brown liquid: oxide concentration 3% by weight) A 2.5% by weight mixed solution was sprayed onto the substrate by a spray nozzle and dried, followed by an O ₂ / N ₂ ratio of 20%. Was subjected to heat treatment (baking) at 500 ° C. for 1 hour in an oxidizing atmosphere. A barrier layer having a thickness of about 50 nm was formed by a single application and heat treatment.

  Next, a platinum catalyst layer was formed on the obtained barrier layer as follows using an ion plating apparatus (AAIF-T12100SB type manufactured by Shinko Seiki Co., Ltd.).

  That is, after removing the oxide film on the surface of the barrier layer by argon ion bombardment (Ar bombardment), a platinum catalyst layer was formed by ion plating. Ar bombardment was performed at an Ar flow rate of 260 sccm, a substrate bias of 1500 V, and a processing time of 10 minutes. In the film forming process, a platinum catalyst layer having a substrate bias of −500 V, an ionization electrode of 50 V, a film forming speed of 0.025 μm / min, an EB voltage of 9 kV, and a film thickness of 0.28 μm (280 nm) was formed.

[Example 2]
In the same manner as in Example 1, a barrier layer having a thickness of 100 nm was formed on a substrate, and a platinum catalyst layer having a thickness of 0.28 μm (280 nm) was formed on the barrier layer.

Comparative Example [Comparative Example 1]
A 50 nm thick barrier layer containing no Ce was formed on the substrate in the same manner as in Example 1 except that CeO ₂ was not added, and a 0.28 μm (280 nm) thick film was formed on the obtained barrier layer. A platinum catalyst layer was formed.

[Comparative Example 2]
A 100 nm-thickness barrier layer not containing Ce was formed on the substrate in the same manner as in Example 1 except that CeO ₂ was not added, and platinum having a thickness of 0.28 μm (280 nm) was formed on the barrier layer. A catalyst layer was formed.

[Comparative Example 3]
A TiN film was used as a barrier layer, and a platinum catalyst layer was formed on the TiN barrier layer. The TiN barrier layer was formed using a cathode arc type ion plating apparatus, and the film thickness was 3 μm. A platinum catalyst layer of 0.3 μm (300 nm) was formed on the formed TiN barrier layer by an ion plating apparatus (AAIF-T12100SB type manufactured by Shinko Seiki Co., Ltd.).

Test method [barrier property test]
The samples of Example 1, Example 2 and Comparative Examples 1 and 2 were heated in a high temperature atmosphere at 550 ° C. for 600 hours to accelerate the environment, and the change in Fe content in the platinum catalyst layer was examined. As an environmental acceleration test machine, a small program electric furnace (model number MMF-1) manufactured by AS ONE Co., Ltd. was used, and the Fe content was EDAX Inc. A manufactured EDX analyzer (model number GENESIS XM2) was used. The test conditions were as follows.

  The test results are shown in the graph of FIG. As is clear from the graph of FIG. 1, Example 1 and Example 2 show that the Fe content in the platinum catalyst layer is less after 600 hours than in Comparative Example 1 and Comparative Example 2. That is, it was confirmed that the barrier layers of Example 1 and Example 2 had little deterioration over time in the barrier function for preventing the migration of impurities from the base material to the platinum catalyst layer.

In addition, although Fe content of Example 1, Example 2, and Comparative Example 1 and Comparative Example 2 heated for 0 hours (before heating) is about 14%, this is a combination of Pt and Y ₂ O ₃ . Since the film thickness was as thin as 0.33 μm to 0.38 μm (330 nm to 380 nm), the Fe component of the underlying SUS316L was partially measured by EDX analysis.

[Adhesion test]
Next, with respect to Example 2, Comparative Example 2, and Comparative Example 3, an adhesion force test of the platinum catalyst layer to the barrier layer was performed. The test apparatus used was an adhesion tester (coating film adhesion tester, Type 0610, manufactured by Cortec Co., Ltd.).

  The dolly attached to the test apparatus was adhered to the platinum catalyst layer using a predetermined epoxy resin adhesive. The sample to which the dolly was adhered was heated in a high-temperature air atmosphere for 1000 hours to accelerate the environment, and the peel strength was measured by an adhesion tester every 50 hours. The high temperature atmosphere temperature was 550 ° C. in Example 2, 500 ° C. and 550 ° C. in Comparative Example 2, and 500 ° C. in Comparative Example 3.

  FIG. 2 shows the test results of Example 2, Comparative Example 1, and Comparative Example 2, and FIG. 3 shows the test results of Comparative Example 3.

  Referring to the graphs of FIG. 2 and FIG. 3, in Comparative Example 3, the adhesive force is extremely reduced after 200 hours have elapsed, but Example 2, Comparative Example 1, and Comparative Example 2 are attached even when 600 hours have elapsed. It can be seen that the wearing force has hardly decreased. From Example 2 and Comparative Example 3, it was found that even if the film thickness was much thinner (100 nm) than the TiN barrier layer (3 μm), the adhesion strength higher than that of the TiN barrier layer was maintained.

  By controlling the film thickness of the barrier layer of the present invention from the above-described barrier property test and adhesion test, even if using yttrium that is more expensive than titanium, at a cost equivalent to or lower than that of the TiN barrier layer, It was confirmed that a barrier layer having better barrier performance and adhesion performance can be formed.

22, 23 Furnace body member 24 Raw material gas inlet 25 Moisture gas outlet 26 Inlet side reflector 27 Outlet side reflector 28a Barrier layer 28b Platinum catalyst layer 30 Fixing screw 31 Spacer

Claims (11)

A reactor main body provided with a gas inlet and a moisture outlet, a barrier layer formed on the inner wall surface of the reactor main body, and a platinum catalyst layer formed on the barrier layer,
The barrier layer is Y ₂ O ₃ 90-99.5% by weight, a metal oxide other than Y ₂ O ₃ , and the standard enthalpy of formation per 1 mol of a single bond between a metal atom and an oxygen atom is −200 kJ / mol. A water-generating reactor comprising 0.5 to 10% by weight of a metal oxide as described below. _2. The water generation reaction according to claim 1, wherein the metal oxide is at least one selected from the group consisting of La ₂ O ₃ , CeO ₂ , Ce ₂ O ₃ , MgO, and ThO _2. Furnace. 2. The water generating reactor according to claim 1, wherein the reactor main body is made of a material having no catalytic activity with respect to hydrogen and oxygen. 2. The moisture generation according to claim 1, further comprising at least one reflector in the reactor main body, wherein the reflector is made of a material having no catalytic activity with respect to hydrogen and oxygen. Reactor. The reflector is fixed to the reactor main body by a fixing screw via a spacer so that at least one of the gas inlet and the moisture outlet is shielded at a predetermined interval, and the spacer and the fixing screw are hydrogenated. The water generating reactor according to claim 4, wherein the water generating reactor is formed of a material having no catalytic activity with respect to oxygen. 6. The water generating reactor according to claim 3, wherein the material having no catalytic activity is an iron-chromium-aluminum alloy, an aluminum alloy, or a copper alloy. 2. The portion having no platinum catalyst layer in the internal space of the reactor main body is covered with a non-catalytic layer made of a material having no catalytic activity with respect to hydrogen and oxygen. The reactor for moisture generation described in 1. At least one reflector is further provided in the reactor main body, and the reflector is covered with a non-catalytic layer made of a material having no catalytic activity with respect to hydrogen and oxygen. Item 2. The water generation reactor according to Item 1. The reflector is fixed to the reactor main body by a fixing screw via a spacer so that at least one of the gas inlet and the moisture outlet is shielded at a predetermined interval, and the spacer and the fixing screw are hydrogenated. The water generating reactor according to claim 9, wherein the reactor is covered with a non-catalytic layer made of a material having no catalytic activity with respect to oxygen. The non-catalytic layer made of a material having no catalytic activity is selected from the group consisting of TiN, TiC, TiCN, TiAlN, Al ₂ O ₃ , Cr ₂ O ₃ , SiO ₂ , CrN, and Y ₂ O _3. The reactor for water generation according to any one of claims 7 to 9, wherein the reactor is formed of at least one material. The water generation reactor according to any one of claims 7 to 9, wherein the non-catalytic layer made of a material having no catalytic activity is formed of the same material as the barrier layer.

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