JP5011925B2 - Method for producing cermet laminate and cermet laminate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a manufacturing method of a cermet laminate capable of directly forming a cermet layer composed of a cermet material containing a metal and metal oxide and having excellent planarity on a base material. <P>SOLUTION: The manufacturing method of the cermet laminate having the cermet layer composed of the cermet material containing the metal and the metal oxide formed on the base material comprises: a metal oxide film forming step of forming a metal oxide film included with two or more metal oxides containing metal elements varying from each other on the base material; and a reducing step of reducing at least one metal oxide among the two or more included in the metal oxide film thereby forming the cermet state containing at least one metal and at least one metal oxide. <P>COPYRIGHT: (C)2008,JPO&amp;INPIT

Description

  The present invention relates to a method for producing a cermet laminate in which a cermet layer containing a metal and a metal oxide is formed on a substrate. More specifically, the cermet layer is directly formed on the substrate. The present invention relates to a method for producing a cermet laminate.

Cermet is a material composed of a metal carbide, boride, or a co-sintered body of an oxide and a metal, and has the advantage of combining the toughness of a metal material and the heat resistance of a ceramic material. The application development is actively studied. Among the cermets, it is expected that application development is expected mainly from cermets made of a co-sintered metal oxide and metal, for example, metals such as Fe, Ni, Co, Cr, Mo, A co-sintered body with a metal oxide such as Al ₂ O ₃ , ZrO ₂ , ThO ₂ corresponds to this.

  The cermet has a specific state in which a metal and a metal oxide are co-sintered, and therefore its production method is limited. As a production method used industrially, a metal and a metal oxide are used. In a suitable combination, etc., there is currently only known a method in which ceramic fine particles and metal powder are subjected to high-pressure press molding and then subjected to high-temperature sintering or high-temperature high-pressure pressing (for example, patent documents) 1).

Here, the cermet is a material that is promising for use as an electrode of a fuel cell, for example, depending on its composition by thinning. Therefore, it is desirable that the cermet can be easily formed into a thin film in order to enable wide-ranging application of the cermet.
However, the above-described cermet manufacturing method has a problem that, after forming a cermet once, there is only a method for forming the cermet into a thin film, and there is no means for thinning the cermet, which is difficult to use as an industrial means. It was.
In addition, since the cermet production method described above uses fine particles as starting materials for both the metal oxide and the metal, it is impossible to form a film having a thickness smaller than the particle diameter of the fine particles, and the flatness is excellent. There was also a problem that it was difficult to form a thin film.

JP 2005-194573 A

  The present invention has been made in view of the above-described problems, and is a cermet laminate that can be directly formed on a base material from a cermet material containing a metal and a metal oxide and having excellent planarity. The main purpose is to provide a method for producing a body.

  In order to solve the above problems, the present invention provides a method for producing a cermet laminate comprising a base material and a cermet layer formed on the base material and including a cermet material containing a metal and a metal oxide. A metal oxide film forming step of forming a metal oxide film containing two or more kinds of metal oxides containing different metal elements on the base material by vapor phase epitaxy or chemical solution method And reducing at least one of the two or more types of metal oxides contained in the metal oxide film to form at least one type of metal and at least one type of metal oxide film. There is provided a method for producing a cermet laminate, comprising a reduction step of converting a metal oxide into a cermet state.

According to the present invention, after the metal oxide film is formed on the substrate by a so-called crystal growth type ceramic thin film formation process called a vapor phase growth method or a chemical solution method in the metal oxide film formation step. The cermet layer can be directly formed on the substrate by bringing the metal oxide film into a cermet state by the reduction step. Moreover, in this invention, the cermet layer excellent in planarity can be formed by forming a cermet layer by such a method.
Therefore, according to the method for producing a cermet laminate of the present invention, a cermet layer made of a cermet material containing a metal and a metal oxide and having excellent planarity can be directly formed on a substrate. .

  In this invention, it is preferable that the said reduction | restoration process is what makes the said metal oxide film the said cermet state by the method of making hydrogen gas contact the said metal oxide film. This is because such a method facilitates uniform reduction of the metal oxide film.

  The present invention is a cermet laminate having a base material and a cermet layer formed on the base material and composed of a cermet material containing a metal and a metal oxide, and the film thickness of the cermet layer is 10 nm. The cermet laminated body characterized by being in the range of-10 micrometers is provided.

  According to the present invention, when the thickness of the cermet layer is within the above range, for example, an electrode for a fuel cell, a cured film on a tool or a substrate, a hard conductive thin film and a transparent conductive thin film, an optical thin film, And the cermet laminated body which can be used suitably as a protective cured film for micromachines, etc. can be obtained.

  The present invention also provides a cermet laminate comprising a base material and a cermet layer formed on the base material and comprising a cermet material containing a metal and a metal oxide, wherein the cermet layer is the cermet material. And a cermet laminated body comprising cermet fine particles having an average particle diameter of 500 nm or less.

  According to the present invention, when the cermet layer is composed of the cermet fine particles, a cermet laminate having a cermet layer having excellent flatness can be obtained.

  The present invention produces an effect that a cermet laminate can be produced by directly forming a cermet layer on a substrate.

  Hereinafter, the manufacturing method and cermet laminated body of the cermet laminated body of this invention are demonstrated in detail.

A. First, a method for producing a cermet laminate according to the present invention will be described. The method for producing a cermet laminate of the present invention is a method for producing a cermet laminate comprising a substrate and a cermet layer formed on the substrate and composed of a cermet material containing a metal and a metal oxide. A metal oxide film forming step of forming a metal oxide film containing two or more kinds of metal oxides containing different metal elements on the base material by a vapor phase growth method or a chemical solution method; The metal oxide film is reduced by reducing at least one metal oxide of two or more kinds of metal oxides contained in the metal oxide film, thereby converting the metal oxide film into at least one metal and at least one metal. And a reduction step of bringing the oxide into a cermet state.

Such a cermet laminate manufacturing method of the present invention will be described with reference to the drawings. FIG. 1 is a schematic view showing an example of the cermet laminate of the present invention. As illustrated in FIG. 1, in the method for producing a cermet laminate of the present invention, first, a metal oxide film in which two kinds of metal compounds containing different metal elements (A, B) are dissolved by a spray device 1. By atomizing the forming solution 2 and bringing the atomized metal oxide film forming solution 2 into contact with the base material 3 heated to a temperature higher than the metal oxide film forming temperature (FIG. 1A). Then, the metal oxide film 4 is formed on the substrate 3 (metal oxide film forming step) (FIG. 1B). The metal oxide film 4 thus formed contains two types of metal oxides (AO, BO) having a metal element contained in the metal compound.
Next, of the two types of metal oxides (AO, BO) contained in the metal oxide film 4, AO is reduced, and the metal oxide film 4 is converted into a metal (A) and a metal oxide (BO). ) In a cermet state (reduction step) (FIG. 1 (c)).
The manufacturing method of the cermet laminated body of this invention manufactures the cermet laminated body 10 in which the cermet layer 5 was formed on the base material 3 by such a process.

  Here, although the example using two types of metal compounds has been described in the above example, the method for producing the cermet laminate of the present invention may use three or more types of metal compounds.

According to the present invention, after the metal oxide film is formed on the substrate by a so-called crystal growth type ceramic thin film formation process called a vapor phase growth method or a chemical solution method in the metal oxide film formation step. The cermet layer can be directly formed on the substrate by bringing the metal oxide film into a cermet state by the reduction step. Moreover, in this invention, the cermet layer excellent in planarity can be formed by forming a cermet layer by such a method.
Therefore, according to the method for producing a cermet laminate of the present invention, a cermet layer made of a cermet material containing a metal and a metal oxide and having excellent planarity can be directly formed on a substrate. .

  The manufacturing method of the cermet laminated body of this invention has a metal oxide film formation process and a reduction process. Hereinafter, these steps will be described in order.

1. Metal Oxide Film Forming Step First, the metal oxide film forming step in the present invention will be described. In the metal oxide film forming step of the present invention, a metal oxide film containing two or more kinds of metal oxides containing different metal elements on the substrate is formed by a vapor phase growth method or a chemical solution method. It is a process of forming.

(1) Method for forming metal oxide film In this step, the method for forming the metal oxide film on the substrate is particularly limited as long as it is a method corresponding to a vapor phase growth method or a chemical solution method. It is not a thing.
Here, the vapor phase growth method is a method of growing a solid layer by adhering and depositing a gaseous compound on a base object by thermal decomposition or reduction. Examples of such a vapor phase growth method include a sputtering method, a CVD method, and an ion plating method.
On the other hand, the chemical solution method is a method in which a metal oxide film forming solution in which two or more kinds of metal compounds containing different metal elements are dissolved is brought into contact with a substrate. Examples of such a chemical solution method include a sol-gel method, a spray pyrolysis method, and a plating method.

  In this step, any one of the vapor phase growth method and the chemical solution method can be preferably used, but the chemical solution method is particularly preferable. By using the chemical solution method, it becomes possible to directly form a cermet layer having excellent flatness, for example, even on a porous substrate, regardless of the type of substrate used in this step. Because. Further, by forming a metal oxide film by a chemical solution method, it becomes easy to adjust the composition of the metal oxide film formed in this step, or after a reduction step described later. This is because it has the advantage that the adhesion between the substrate and the cermet layer is excellent.

  Hereinafter, a method for forming a metal oxide film using such a chemical solution method will be described in detail.

a. First, the metal oxide film forming solution will be described. The metal oxide film forming solution is a solution in which two or more metal compounds having different metal elements are dissolved, and usually contains two or more metal compounds and a solvent for dissolving them. It is done.

i. Metal Compound The metal compound used in the metal oxide film forming solution will be described. The said metal compound forms a metal oxide film by being heated more than the metal oxide film formation temperature mentioned later.

Here, in the present step, the “metal oxide film formation temperature” refers to a temperature at which a metal element is combined with oxygen in the metal compound and a metal oxide film can be formed on a substrate. It varies greatly depending on the type of metal compound and the composition of the metal oxide film forming solution such as a solvent.
Such “metal oxide film formation temperature” can be measured by the following method. That is, the lowest group capable of forming a metal oxide film is prepared by actually preparing a solution for forming a metal oxide film in which a desired metal compound is dissolved and changing the heating temperature of the base material. The material heating temperature is measured. This lowest substrate heating temperature can be set as the “metal oxide film forming temperature” in this step. At this time, whether or not the metal oxide film is formed is usually judged from the result obtained from an X-ray diffraction apparatus (Rigaku, RINT-1500). In the case of an amorphous film having no crystallinity, photoelectron spectroscopy is performed. It shall judge from the result obtained from the analyzer (the product made by VG Scientific, ESCALAB 200i-XL).

The two or more types of metal compounds used in this step are not particularly limited as long as they contain different metal elements and can be dissolved in a solvent described later.
Examples of such metal compounds include metal salts and organometallic compounds.
Here, the “organometallic compound” in this step is a group in which an organic substance is coordinated to a metal ion, or an aggregate in which another kind of ion, molecule, or polyatomic ion is bonded to a central atom. It shall mean a so-called metal complex.

Examples of the metal element include Mg, Al, Si, Ti, V, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Ag, In, Sn, Ce, Sm, Pb, La, Hf, Examples include Sc, Gd, Ca, Cr, Ga, Sr, Nb, Mo, Pd, Sb, Te, Ba, W, and Ta. In this step, any two or more of these metal elements can be used in combination. In particular, in this step, a metal oxide film formed by this step is used in the reduction step described later. It is preferable to use a combination of metal elements having a chemical potential difference of 10 kcal or more, more preferably 20 kcal or more, and even more preferably 50 kcal or more when forming a metal oxide at the temperature at which the metal oxide is brought into the cermet state. By using the above metal elements in such a combination, when the metal oxide film is reduced in the reduction step described later, at least one of two or more kinds of metal oxides contained in the metal oxide film is selectively used. This is because it becomes easy to reduce the amount to
Here, the difference in chemical potential of oxygen can be obtained by drawing an Ellingham diagram for each metal element.

  As such a combination of metal elements, for example, at least one metal element selected from the group consisting of Cu, Fe, Ni, Pb, Co, Mo, and Cr, and Ca, Mg, Li, Al, A combination with at least one metal element selected from the group consisting of Ti, Si, V, Mn, and Zr can be exemplified. Among these, preferable combinations to be employed in this step include, for example, Ni and Zr, Fe and Al, Cu and Ti, Pb and Ca, Co and Si, Mo and V, Cr and Li, and the like.

  Examples of the metal salt used in this step include chlorides, nitrates, sulfates, perchlorates, acetates, phosphates and bromates containing the above metal elements. Of these, chloride, nitrate, and acetate are preferably used in this step. This is because these compounds are easily available as general-purpose products.

  Examples of the organometallic compound used in this step include magnesium diethoxide, metal acetylacetonate, calcium acetylacetonate dihydrate, calcium di (methoxyethoxide), calcium gluconate monohydrate, Calcium citrate tetrahydrate, calcium salicylate dihydrate, titanium lactate, titanium acetylacetonate, tetraisopropyl titanate, tetranormal butyl titanate, tetra (2-ethylhexyl) titanate, butyl titanate dimer, titanium bis (ethylhexoxy) bis (2-ethyl-3-hydroxyhexoxide), diisopropoxytitanium bis (triethanolaminate), dihydroxybis (ammonium lactate) titanium, diisopropoxytitanium bis ( Tylacetoacetate), titanium peroxosodium citrate tetrahydrate, dicyclopentadienyl iron (II), iron (II) lactate trihydrate, iron (III) acetylacetonate, cobalt (II) acetylacetate Narate, nickel (II) acetylacetonate dihydrate, copper (II) acetylacetonate, copper (II) dipivaloylmethanate, copper (II) ethylacetoacetate, zinc acetylacetonate, zinc lactate trihydrate , Zinc salicylate trihydrate, zinc stearate, strontium dipivaloylmethanate, yttrium dipivaloylmethanate, zirconium tetra-n-butoxide, zirconium (IV) ethoxide, zirconium normal propyrate, zirconium normal butyrate Rate, zirconium tetraacetylacetonate, zirconium monoacetylacetonate , Zirconium acetylacetonate bisethylacetoacetate, zirconium acetate, zirconium monostearate, penta-n-butoxyniobium, pentaethoxyniobium, pentaisopropoxyniobium, tris (acetylacetonato) indium (III), 2-ethylhexanoic acid Indium (III), tetraethyltin, dibutyltin oxide (IV), tricyclohexyltin (IV) hydroxide, lanthanum acetylacetonate dihydrate, tri (methoxyethoxy) lanthanum, pentaisopropoxytantalum, pentaethoxytantalum, tantalum (V) Ethoxide, cerium (III) acetylacetonate n-hydrate, lead (II) citrate trihydrate, lead cyclohexanebutyrate and the like. Among these, in this step, magnesium diethoxide, metal acetylacetonate, calcium acetylacetonate dihydrate, titanium lactate, titanium acetylacetonate, tetraisopropyl titanate, tetranormal butyl titanate, tetra (2-ethylhexyl) Titanate, butyl titanate dimer, diisopropoxy titanium bis (ethylacetoacetate), iron (II) lactate trihydrate, iron (III) acetylacetonate, zinc acetylacetonate, zinc lactate trihydrate, strontium dipivalo Ilmethanate, pentaethoxyniobium, tris (acetylacetonato) indium (III), indium (III) 2-ethylhexanoate, tetraethyltin, dibutyltin oxide (IV), lanthanum acetylacetonate dihydrate, It is preferred to use (methoxyethoxy) lanthanum, cerium (III) acetylacetonate n-hydrate.

What is necessary is just to adjust arbitrarily the density | concentration of the said metal compound in the solution for metal oxide film formation used for this process according to the kind etc. of a metal compound. In particular, when a metal salt is used as the metal compound, it is preferably in the range of 0.001 mol / L to 2 mol / L, particularly preferably in the range of 0.01 mol / L to 1 mol / L.
On the other hand, when an organometallic compound is used as the metal compound, it is preferably in the range of 0.001 mol / L to 2 mol / L, and particularly preferably in the range of 0.01 mol / L to 1 mol / L. . This is because if the concentration is below the above range, it takes time to form the metal oxide film, which may not be industrially suitable. Moreover, it is because there exists a possibility that a metal oxide film with a uniform film thickness cannot be obtained when the concentration is above the above range.

ii. Solvent The solvent used in this step is not particularly limited as long as it can dissolve the above-described metal compound at a desired concentration. As such a solvent, for example, when a metal salt is used as the metal compound, lower alcohols having a total carbon number of 5 or less such as water, methanol, ethanol, isopropyl alcohol, propanol, butanol, toluene, and the like. A mixed solvent etc. can be mentioned.
In addition, when an organometallic compound is used as the metal compound, water, the above-described lower alcohol, toluene, and a mixed solvent thereof can be given.

  In this step, the above solvents may be used in combination. For example, when using a metal compound that has low solubility in water but high solubility in organic solvents, and a reducing agent that has low solubility in organic solvents but high solubility in water, water and organic By mixing with a solvent, both can be dissolved to obtain a uniform metal oxide film forming solution.

iii. Oxidizing agent and reducing agent In this step, it is preferable that the metal oxide film forming solution contains an oxidizing agent and / or a reducing agent. This is because the metal oxide film can be formed at a lower temperature in this step because the metal oxide film forming solution contains an oxidizing agent and a reducing agent. Moreover, it is because the heating temperature of the base material in this process can be lowered by this, and a highly transparent metal oxide film can be formed.

  Here, the oxidizing agent has a function of promoting oxidation of metal ions formed by dissolving the above-described metal compound. By changing the valence of metal ions, an environment in which a metal oxide film can be easily formed can be obtained, and a metal oxide film can be obtained at a lower substrate heating temperature as compared with conventional methods.

  The oxidizing agent used in this step is not particularly limited as long as it can be dissolved in the above-described solvent and can promote the oxidation of metal ions. Examples of such an oxidizing agent include hydrogen peroxide, sodium nitrite, potassium nitrite, sodium bromate, potassium bromate, silver oxide, dichromic acid, and potassium permanganate. Among these, hydrogen peroxide or sodium nitrite can be mentioned in this step.

  When the oxidizing agent is used in this step, the concentration of the oxidizing agent contained in the metal oxide film forming solution varies depending on the type of the oxidizing agent, but is usually 0.001 mol / L to 1 mol. / L is preferable, and it is particularly preferable to be within a range of 0.01 mol / L to 0.1 mol / L. This is because if the concentration is not more than the above range, the effect of lowering the substrate heating temperature due to the inclusion of the oxidizing agent may not be sufficiently exhibited. Further, if the concentration is in the above range or more, there is no great difference in the obtained effect, which is not preferable in terms of cost.

  On the other hand, the reducing agent emits electrons by a decomposition reaction, generates hydroxide ions by water electrolysis, and has a function of raising the pH of the metal oxide film forming solution. Since the pH of the solution for forming a metal oxide film is increased, an environment in which a metal oxide film can be easily formed can be obtained, so that the metal oxide film can be obtained at a lower substrate heating temperature.

  The reducing agent used in this step is not particularly limited as long as it can be dissolved in a solvent described later and can emit electrons by a decomposition reaction. Examples of such a reducing agent include borane complexes such as borane-tert-butylamine complex, borane-N, N diethylaniline complex, borane-dimethylamine complex, borane-trimethylamine complex, sodium cyanoborohydride, hydroxylation. Mention may be made of sodium boron. In particular, it is preferable to use a borane complex in this step.

  When the reducing agent is used in this step, the concentration of the reducing agent contained in the metal oxide film forming solution varies depending on the type of the reducing agent, but is usually 0.001 mol / L to 1 mol. / L is preferable, and it is particularly preferable to be within a range of 0.01 mol / L to 0.1 mol / L. This is because if the concentration is below the above range, the effect of lowering the substrate heating temperature by adding the reducing agent may not be sufficiently exhibited. Further, if the concentration is in the above range or more, there is no great difference in the obtained effect, which is not preferable in terms of cost.

In this step, the reducing agent and the oxidizing agent may be used in combination. This is because even when the reducing agent and the oxidizing agent are used in combination, the metal oxide film can be obtained at a lower substrate heating temperature as compared with the conventional method.
In this step, when the reducing agent and the oxidizing agent are used in combination, the combination of the reducing agent and the oxidizing agent is particularly limited as long as the combination can reduce the substrate heating temperature to a desired temperature. Is not to be done. Examples of such a combination include a combination of hydrogen peroxide or sodium nitrite and an arbitrary reducing agent, a combination of an arbitrary oxidizing agent and a borane complex, and the like. In particular, in this step, a combination of hydrogen peroxide and a borane complex is preferable.

iv. Additives The metal oxide film forming solution used in this step may contain additives such as ceramic fine particles, an auxiliary ion source, and a surfactant.
Hereinafter, these additives will be described in order.

(Ceramic fine particles)
When the ceramic fine particles are contained in the metal oxide film forming solution, a metal oxide film can be formed so as to surround the ceramic fine particles, and a mixed film of different ceramics can be obtained. This has the advantage that the volume of the film can be increased.

  The ceramic fine particles used in this step are not particularly limited as long as the above object can be achieved. Examples of such ceramic fine particles include ITO, metal oxide, zirconium oxide, silicon oxide, titanium oxide, tin oxide, cerium oxide, calcium oxide, manganese oxide, magnesium oxide, and titanic acid. There may be mentioned fine particles made of barium or the like.

  In addition, when using the said ceramic fine particle in this process, content of the ceramic fine particle in the said metal oxide film formation solution will be suitably adjusted according to the characteristic of the member to be used.

(Auxiliary ion source)
When the auxiliary ion source is contained in the metal oxide film forming solution, it reacts with electrons generated by thermal decomposition of the reducing agent to generate hydroxide ions, and the metal oxide film It has a function of increasing the pH of the forming solution to make it easy to form a metal oxide film. For this reason, a metal oxide film can be obtained at a lower substrate heating temperature by adding an auxiliary ion source to the metal oxide film forming solution as compared with the conventional method.

  Examples of the auxiliary ion source used in this step include chlorate ion, perchlorate ion, chlorite ion, hypochlorite ion, bromate ion, hypobromate ion, nitrate ion, and nitrite ion. An ionic species selected from the group consisting of:

  Moreover, when using the said ceramic fine particle in this process, content of the auxiliary ion source in the said metal oxide film formation solution will be suitably adjusted according to the metal compound, reducing agent, etc. to be used.

(Surfactant)
The surfactant acts on the interface between the metal oxide film forming solution and the substrate surface by being contained in the metal oxide film forming solution. The contact area between the substrate and the substrate surface can be improved, and a uniform metal oxide film can be obtained.

  Examples of the surfactant used in this step include Surfinol 485, Surfinol SE, Surfinol SE-F, Surfinol 504, Surfinol GA, Surfinol 104A, Surfinol 104BC, Surfinol 104PPM, Surfinol 104E. Surfynol series such as Surfinol 104PA (all manufactured by Nissin Chemical Industry Co., Ltd.), NIKKOL AM301, NIKKOL AM313ON (all manufactured by Nikko Chemical Co., Ltd.), and the like.

  Moreover, when using the said surfactant in this process, content of the surfactant in the said solution for metal oxide film formation will be suitably adjusted according to the metal compound and reducing agent to be used.

b. Next, a method for forming a metal oxide film on the substrate by bringing the metal oxide film forming solution into contact with the substrate will be described.

  In this step, as a method of forming a metal oxide film on the base material by bringing the metal oxide film forming solution into contact with the base material, a metal oxide having a desired flatness is formed on the base material. The method is not particularly limited as long as it is a method capable of forming a physical film. As such a method, for example, a method in which the metal oxide film forming solution is brought into contact with a substrate heated to a temperature higher than the metal oxide film forming temperature, and the metal oxide film forming solution is used as the base. Examples thereof include a method in which the substrate is heated to a temperature higher than the metal oxide film formation temperature after being brought into contact with the material. Any of these methods can be suitably used in this step.

The method for bringing the metal oxide film forming solution into contact with the base material is not particularly limited as long as the metal oxide film forming solution can be uniformly brought into contact with the surface of the base material. is not. As such a method, for example, the metal oxide film forming solution is atomized using a spray device, and the atomized metal oxide film forming solution is contacted with a substrate, or the metal oxide film Examples thereof include a method of immersing the substrate in the forming solution and pulling it up. Any of these contact methods can be preferably used in this step, but the metal oxide film forming solution is atomized using a spray device, and the atomized metal oxide film is formed. It is preferable to use a method in which a solution for contact is brought into contact with a substrate. This is because by using such a method, a metal oxide film made of fine particles can be formed, so that it is easy to form a metal oxide having excellent planarity by this step.
Hereinafter, such a contact method will be described in detail.

  The spray device is not particularly limited as long as it is a device having a spray system capable of forming the above-described metal oxide film forming solution into a mist shape composed of droplets of a desired size. Examples of such a spray method include an air spray method, an airless spray method, a rotating fine particle spray method, and an ultrasonic spray method.

  Further, the nozzle diameter of the spray device is not particularly limited as long as it is within a range where a desired metal oxide film can be obtained, but it is usually preferably within a range of 10 μm to 1000 μm, Especially, it is preferable to exist in the range of 50 micrometers-500 micrometers, and it is especially preferable to exist in the range of 100 micrometers-300 micrometers.

  As a method of bringing the metal oxide film forming solution atomized by the spray device into contact with the substrate, the metal oxide film forming solution atomized by the spray device described above and the substrate The method is not particularly limited as long as it can be uniformly contacted. Such methods include, for example, a method in which an atomized metal oxide film forming solution is sprayed on a substrate and a space in which the atomized metal oxide film forming solution is mist-like. And a method of passing the material.

  When using the method of spraying the atomized metal oxide film forming solution on the substrate as the contact method, the diameter of the droplets of the atomized metal oxide film forming solution is as follows: If it is in the range which does not reduce the temperature of a base material at the time of contact with, it will not specifically limit. Especially in this process, it is preferable to exist in the range of 0.1 micrometer-1000 micrometers, and it is further preferable to exist in the range of 0.5 micrometer-300 micrometers. This is because when the droplet diameter is within the above range, the substrate temperature does not decrease when the droplet contacts the substrate, and a uniform metal oxide film can be obtained.

  Further, the discharge amount of the atomized metal oxide film-forming solution is also particularly limited as long as the temperature of the base material is not lowered when the metal oxide film-forming solution contacts the base material. Is not to be done. In particular, in this step, it is preferably in the range of 0.001 L / min to 1 L / min, more preferably in the range of 0.001 L / min to 0.05 L / min. It is preferably within a range of 01 L / min to 0.05 L / min. This is because if it exceeds the above range, the substrate temperature may be lowered. In addition, when it is less than the above range, it takes time to form the metal oxide film, which is not preferable in terms of cost.

  The method for spraying the atomized metal oxide film forming solution onto the substrate is not particularly limited as long as it can form a desired metal oxide film on the substrate. Examples of such a method include a method of spraying on a fixed substrate and a method of spraying on a moving substrate.

  As a method of spraying on the fixed base material, for example, as shown in FIG. 2, the fixed base material 3 is heated to a temperature equal to or higher than the metal oxide film formation temperature, A method of spraying the atomized metal oxide film forming solution 2 using the spray device 1 can be mentioned.

  On the other hand, as a method of spraying on the moving base material, for example, as shown in FIG. 3, the base material 3 is continuously moved using rollers 6 to 8 heated to a metal oxide film forming temperature or higher. And a method of spraying the atomized metal oxide film forming solution 2 using the spray device 1 on the base material 3. This method has an advantage that a metal oxide film can be continuously formed.

  Moreover, in the method of spraying the atomized metal oxide film forming solution onto the substrate, the shape of the substrate used is not particularly limited as long as it can be sprayed by a spray device. For example, a plate-like or cylindrical substrate can be used. When the cylindrical base material is used, a metal oxide film can be formed on the inner surface of the cylinder if the spray device can enter the cylinder.

  On the other hand, when the method of passing the substrate through the space in which the atomized metal oxide film forming solution is mist-shaped is used as the contact method, the atomized metal oxide film forming solution is used. The diameter of the droplet is not particularly limited as long as the temperature of the substrate is not lowered. Especially in this process, it is preferable to exist in the range of 0.1 micrometer-300 micrometers, and it is preferable to exist in the range of 1 micrometer-100 micrometers especially. This is because if the droplet diameter is within the above range, the substrate temperature can be prevented from decreasing, and a uniform metal oxide film can be obtained.

  Although it does not specifically limit as a method to pass a base material in the space which made the atomized metal oxide film formation solution the mist form, For example, as shown in FIG. And a method of allowing the substrate 3 heated to a temperature equal to or higher than the metal oxide film forming temperature to pass through the space in which the metal oxide film forming solution 2 is made into a mist using the above.

  In addition, the temperature for heating the substrate is not particularly limited as long as it is equal to or higher than the metal oxide film formation temperature. The specific temperature of the metal oxide film formation temperature varies depending on the type of metal compound and the composition of the metal oxide film formation solution such as a solvent. Or when not adding a reducing agent, it is preferable that it is normally within the range of 400 to 600 degreeC, and it is preferable that it is especially within the range of 450 to 550 degreeC. On the other hand, when an oxidizing agent and / or a reducing agent is added to the metal oxide film forming solution, it is usually preferably in the range of 150 ° C to 400 ° C, and in particular, in the range of 300 ° C to 400 ° C. Preferably there is.

  Furthermore, the method for heating the substrate is not particularly limited as long as the substrate can be heated to the metal oxide film formation temperature or higher. As such a method, a surface heating method for heating the substrate from the film formation surface side on which the metal oxide film is formed, a back surface heating method for heating the substrate from the surface opposite to the film formation surface, and The double-sided heating method which heats a base material from both surfaces of the said film-forming surface and its opposite surface can be mentioned. In this step, any of the above surface heating method, back surface heating method, and double-sided heating method can be suitably used.

Here, the surface heating method is a case where the thickness of the base material is large, or the shape of the base material is not a flat surface but has an uneven shape, or a shape such as a mesh shape. In addition, there is an advantage that the film-forming surface of the substrate can be easily heated to a temperature higher than the metal oxide film forming temperature.
Moreover, the said back surface heating method has the advantage that implementation is easy.
Furthermore, since the above-mentioned both-side heating method can reduce the difference in coefficient of thermal expansion between both sides of the base material, it has the advantage that deformation of the base material during heating can be prevented.

Examples of the heating method for heating the substrate include a convection heating method, a conduction heating method, and a radiant heating method, and any heating method can be preferably used in this step.
Here, the convection heating method is a method in which air, gas, liquid, or the like is used as a medium, and the medium is heated by bringing the medium into contact with the substrate.
The conductive heating method is a method in which a heat source is brought into direct contact with a substrate without using a medium, and the substrate is heated by heat conduction from the heat source.
Furthermore, the radiant heating method is a method of heating by irradiating a base material with an electromagnetic wave that induces molecular vibrations.

  In addition, as a heating apparatus of a base material, a hot plate, an infrared heater, etc. can be illustrated, for example. Examples of the infrared heater include a short wavelength infrared heater, a medium wavelength infrared heater, a halogen heater, and a carbon heater.

(2) Base material Next, the base material used for this process is demonstrated. The base material used in this step is one in which a metal oxide film is formed on the surface in this step.

  The substrate used in this step is not particularly limited as long as it has heat resistance that can withstand the “metal oxide film formation temperature”. Such a base material may be a flexible material having flexibility or a rigid material having no flexibility.

  Examples of the material constituting the base material used in this step include glass, SUS, a metal plate, a ceramic substrate, and a heat resistant plastic. In particular, in this step, it is preferable to use glass, SUS, a metal plate, or a ceramic substrate. This is because these materials are versatile and have sufficient heat resistance.

  Moreover, the form of the base material used in this step is not particularly limited, and examples thereof include those having a smooth surface, those having a fine structure, those having holes, and those having grooves. It may be porous or provided with a porous film. In particular, in this step, those having a smooth surface, those having a fine structure, those having grooves, those that are porous, and those having a porous film are preferably used.

(3) Others In this step, the formed metal oxide film may be cleaned. The cleaning of the metal oxide film is performed to remove impurities present on the surface of the metal oxide film, for example, a method of cleaning using a solvent used in the metal oxide film forming solution. Etc.

2. Reduction Step Next, the reduction step in the present invention will be described. In the reduction step of the present invention, the metal oxide film is reduced to at least one metal by reducing at least one of the two or more metal oxides contained in the metal oxide film. And a cermet state containing at least one kind of metal oxide.

  As the reduction mode of the two or more types of metal oxides in this step, at least one type of metal oxide is reduced according to the type or combination of two or more types of metal oxides contained in the metal oxide film. There is no particular limitation as long as it can be performed. Such a reduction mode may be a mode in which only one type of metal oxide is selectively reduced among the above two or more types of metal oxides, and two or more types of metal oxides are reduced. It is also possible to use this mode.

  The reduction method in this step is not particularly limited as long as the desired metal oxide contained in the metal oxide film can be reduced to a desired level. Examples of such a reduction method include a method of bringing a metal oxide film into contact with hydrogen gas, carbon monoxide gas, or carbon C. In particular, in this step, it is preferable to use a method of bringing hydrogen gas into contact with the metal oxide film. This is because such a method facilitates uniform reduction of the metal oxide film.

3. Cermet laminated body Next, the cermet laminated body manufactured by this invention is demonstrated. The cermet laminated body manufactured by this invention has a base material and the cermet layer which is formed on a base material and consists of cermet materials.
Here, the cermet layer is formed by partially reducing the metal oxide in the reduction step after the metal oxide film is once formed in the metal oxide film formation step. In other words, the cermet layer is formed by removing a part of the oxygen component from the metal oxide film formed by the metal oxide film forming step. For this reason, the said cermet layer formed by this invention turns into a porous body which has a micro void | hole in the location from which the oxygen component was removed. And the porosity of the said porous body can be arbitrarily adjusted with the composition of the solution for metal oxide film formation mentioned above, and the grade of the reduction | restoration in the said reduction | restoration process.
Therefore, it can be said that the method for producing a cermet laminate of the present invention is also characterized in that such a porous cermet layer can be formed.

  In addition, about the specific aspect of the cermet laminated body manufactured by the manufacturing method of the cermet laminated body of this aspect, since the example is demonstrated in "B. cermet laminated body" mentioned later, description here is abbreviate | omitted.

B. Cermet Laminate Next, the cermet laminate of the present invention will be described. The cermet laminated body of this invention has a base material and the cermet layer comprised on the said base material and comprised from the cermet material containing a metal and a metal compound.

  Such a cermet laminate of the present invention will be described with reference to the drawings. FIG. 5 is a schematic cross-sectional view showing an example of the cermet laminate of the present invention. As illustrated in FIG. 5, the cermet laminate 10 of the present invention has a base material 3 and a cermet layer 5 formed on the base material 3. In the above example, the cermet layer 5 is composed of a cermet material containing a metal and a metal oxide.

The cermet laminated body of this invention can be divided into two aspects according to the aspect of the said cermet layer.
Hereinafter, the cermet laminate of the present invention will be described separately for each embodiment.

B-1: Cermet laminate of the first aspect First, the cermet laminate of the first aspect of the present invention will be described. The cermet laminated body of this aspect is characterized in that the thickness of the cermet layer is in the range of 10 nm to 10 μm. Moreover, the cermet laminated body of this aspect has the advantage that the cermet laminated body which can be used suitably as an electrode for fuel cells can be obtained, for example.

The cermet laminated body of this aspect has a base material and a cermet layer. Hereinafter, each structure of the cermet laminated body of this aspect is demonstrated in detail.
In addition, about the base material used for this aspect, since it is the same as that of what was demonstrated in the item of the said "A. manufacturing method of a cermet laminated body", description here is abbreviate | omitted.

1. Cermet Layer The cermet layer in this embodiment will be described. The cermet layer in this embodiment has a thickness in the range of 10 nm to 10 μm.

The thickness of the cermet layer in this embodiment is not particularly limited as long as it is within the above range, but is preferably within a range of 100 nm to 10 μm, and particularly preferably within a range of 500 nm to 5 μm. .
The thickness of the cermet layer can be determined by measuring with the scanning electron microscope or the transmission electron microscope.

  Although the cermet material which comprises the said cermet layer contains a metal and a metal oxide, as an aspect of such a combination of a metal and a metal oxide, at least 1 type of metal and at least 1 type of metal If it is the aspect with which the oxide was combined, it will not specifically limit. As such an aspect, an aspect in which one kind of metal and one kind of metal oxide are combined, an aspect in which one kind of metal and two or more kinds of metal oxides are combined, two or more kinds of metals and 1 An embodiment in which two kinds of metal oxides are combined and an embodiment in which two or more kinds of metals and metal oxides are combined can be exemplified. In this aspect, any of these aspects can be used suitably. Moreover, the metal element which comprises the said metal, and the metal element contained in the said metal oxide may be in common.

Moreover, it does not specifically limit as a specific combination of the said metal and metal oxide, According to the use etc. of the cermet laminated body of this aspect, it can select arbitrarily. In particular, in this embodiment, the combination of the metal and the metal oxide has a chemical potential of oxygen when the metal oxide is generated from the metal and a chemical potential of oxygen when the metal oxide is generated. The difference is preferably 10 kcal or more, more preferably 20 kcal or more, and still more preferably 50 kcal or more. Thereby, it becomes easy to manufacture the cermet laminated body of this invention using the manufacturing method of the said cermet laminated body of this invention.
Here, the chemical potential of the oxygen can be obtained by drawing an Ellingham diagram for each metal element. Moreover, although the said chemical potential has temperature dependence, in this invention, the chemical potential in arbitrary temperature should just have the difference of the said range.

As such a combination of metal and metal oxide, a metal composed of at least one metal element selected from the group consisting of Cu, Fe, Ni, Pb, Co, Mo, and Cr, and Ca, Mg, A combination of metal oxides composed of at least one metal element selected from the group consisting of Li, Al, Ti, Si, V, Mn, and Zr can be exemplified. Among these, preferable combinations to be adopted in this embodiment include, for example, Ni and ZrO ₂ , Fe and Al ₂ O ₃ , Cu and TiO ₂ , Pb and CaO, Co and SiO ₂ , Mo and V ₂ O ₃ , Cr And Li ₂ O.

  In addition, the form of the cermet layer in this aspect may be a dense body having no pores, or may be a porous body having pores.

2. Other Applications of the cermet laminate of this embodiment include, for example, electrodes for fuel cells, cured films on tools and substrates, conductive thin films, transparent conductive thin films, optical thin films, or protective cured films for micromachines, etc. Can be mentioned.

  Moreover, the cermet laminated body of this aspect can be manufactured by the method demonstrated in the term of the said "A. manufacturing method of a cermet laminated body", for example.

B-2: Cermet Laminate of Second Aspect Next, the cermet laminate of the second aspect of the present invention will be described. The cermet laminate of the second aspect is characterized in that the cermet layer is composed of a cermet material containing a metal and a metal oxide, and is composed of cermet fine particles having an average particle diameter of 500 nm or less, Thereby, it has the advantage which can obtain the cermet laminated body which has a cermet layer excellent in planarity.

The cermet laminated body of this aspect has a base material and a cermet layer. Hereinafter, each structure of the cermet layer of this aspect is demonstrated in detail.
In addition, about the base material used for this aspect, since it is the same as that of what was demonstrated in the term of the above-mentioned "A. manufacturing method of a cermet layer", description here is abbreviate | omitted.

1. Cermet layer The cermet layer used in this embodiment will be described. The cermet layer used in this embodiment is made of a cermet material containing a metal and a metal oxide, and is made of cermet fine particles having an average particle diameter of 500 nm or less.

The cermet fine particles constituting the cermet layer in the present embodiment are not particularly limited as long as the particle diameter is in the above range, but it is preferably in the range of 10 nm to 500 nm, particularly in the range of 10 nm to 100 nm. It is preferable to be within.
Here, the said particle diameter can be calculated | required from a SEM photograph.

The cermet material constituting the cermet fine particles contains a metal and a metal oxide. As an embodiment of a combination of such a metal and a metal oxide, at least one metal and at least one metal are used. If it is the aspect with which the oxide was combined, it will not specifically limit.
Here, the combination of the metal and the metal oxide used in this embodiment is the same as the embodiment described in the section “B-1: Cermet laminate of the first embodiment”. Description is omitted.

Moreover, although the thickness of the cermet layer in this aspect can be arbitrarily determined according to the use etc. of the cermet laminated body of this aspect. In particular, in this embodiment, it is preferably in the range of 100 nm to 10 μm, more preferably in the range of 500 nm to 5 μm, and particularly preferably in the range of 500 nm to 3 μm. This is because, when the thickness of the cermet layer is within the above range, for example, the cermet laminate of this embodiment can be made suitable as an electrode for a fuel cell.
In addition, since the measuring method of the thickness of the said cermet layer is the same as that of what was described in the term of the said "B-1: the cermet laminated body of a 1st aspect", description here is abbreviate | omitted.

  Furthermore, the form of the cermet layer in this embodiment may be a dense body having no pores, or may be a porous body having pores.

2. Others The use of the cermet laminate of this embodiment is the same as that described in the section “B-1: Cermet laminate of the first embodiment”, and the description thereof is omitted here.

  Moreover, the cermet laminated body of this aspect can be manufactured by the method demonstrated in the term of the said "A. manufacturing method of a cermet laminated body", for example.

  The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the present invention has substantially the same configuration as the technical idea described in the claims of the present invention, and any device that exhibits the same function and effect is the present invention. It is included in the technical scope of the invention.

  Hereinafter, the present invention will be specifically described with reference to examples.

  In this example, an alumina plate (150 mm × 150 mm, thickness 1 mm) was used as the base material.

  First, yttrium nitrate (Kanto Chemical Co., Ltd.) 0.008 mol / L, zirconium acetylacetonate (Kanto Chemical Co., Ltd.) 0.1 mol / L, nickel acetylacetonate (Kanto Chemical Co., Ltd.) 0.05 mol / L 1 L of the solution (the solvent was ethanol 55%, toluene 40%, water 5%) was adjusted to obtain a metal oxide film forming solution.

  1000 mL of the metal oxide film-forming solution was sprayed on the base material using an ultrasonic neplyzer (manufactured by OMRON) to obtain a metal oxide film containing nickel oxide and YSZ. When the said metal oxide film was measured using the X-ray-diffraction apparatus (the Rigaku make, RINT-1500), it confirmed that nickel oxide and YSZ had formed.

  Next, the metal oxide film obtained by the above method was brought into contact with hydrogen gas for 2 hours at a temperature of 600 ° C., and only nickel oxide was reduced to obtain metallic nickel. The film after the reduction was measured using an X-ray diffractometer (Rigaku, RINT-1500), and it was confirmed that metallic nickel and YSZ were formed. Moreover, it was confirmed by TEM (transmission electron microscope) observation that metallic nickel and YSZ were in a cermet state. From the SEM observation, the constituting fine particles had an average of 15 nm.

It is the schematic which shows an example of the cermet laminated body of this invention. It is the schematic which shows the other example of the manufacturing method of the cermet laminated body of this invention. It is the schematic which shows the other example of the manufacturing method of the cermet laminated body of this invention. It is the schematic which shows the other example of the manufacturing method of the cermet laminated body of this invention. It is the schematic which shows an example of the cermet laminated body of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Spray apparatus 2 ... Solution for metal oxide film formation 3 ... Base material 4 ... Metal oxide film 5 ... Cermet film 6-8 ... Roller 10 ... Cermet laminated body

Claims (2)

A method for producing a cermet laminate comprising a base material and a cermet layer formed of the cermet material formed on the base material and containing a metal and a metal oxide,
A metal oxide film forming step of forming a metal oxide film containing two or more kinds of metal oxides containing different metal elements on the substrate by vapor phase growth;
By reducing at least one metal oxide of two or more metal oxides contained in the metal oxide film, the metal oxide film is reduced to at least one metal and at least one metal oxide. And a reduction step for forming the cermet layer in a cermet state containing a product,
A combination of different metal elements contained in each of the two or more metal oxides is Fe and Al, Cu and Ti, Pb and Ca, Co and Si, Mo and V, or Cr and Li,
The method for producing a cermet laminate, wherein the cermet layer is formed with a thickness within a range of 10 nm to 5 μm.   2. The cermet laminate according to claim 1, wherein the reduction step is to bring the metal oxide film into the cermet state by a method of bringing hydrogen gas into contact with the metal oxide film. Method.

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