JP7014353B2 - Crystalline laminated structure - Google Patents

Description

The present invention relates to a novel crystalline laminated structure useful for manufacturing a separator for a fuel cell, which requires conductivity.

The solid polymer type fuel cell separator has electrical conductivity, electrically connects each single cell of the fuel cell, collects the energy (electricity) generated in each single cell, and collects liquid or gas. The flow path is formed, and has a role of supplying fuel gas and oxidizing gas into the battery surface and discharging water generated on the cathode side from the fuel cell together with air after the reaction. Further, the separator is also required to have characteristics such as airtightness for preventing mixing of fuel gas and air and corrosion resistance in a power generation environment.

Examples of the material used for the separator include carbon-based materials and metal materials. Separator using a carbon-based material is excellent in corrosion resistance, but has a problem in conductivity, and a certain thickness is required to obtain sufficient strength and airtightness, so that the size and thickness are reduced. It is a factor that hinders. Further, carbon-based materials have a problem that material cost and processing cost are high. On the other hand, a separator using a metal material can be formed thin because there is no problem in terms of strength and airtightness, but it is prone to corrosion and has a problem in terms of corrosion resistance. As a metal separator having relatively excellent corrosion resistance, a separator using stainless steel has been studied. In stainless steel separators, a passivation film is usually naturally formed on the surface of the stainless steel material, and this passivation film causes an increase in contact resistance. Further, even stainless steel has a drawback that the metal is ionized and eluted due to the influence of corrosive substances (strong acids) generated in the operating environment of a fuel cell or the like. Therefore, it is necessary to further impart corrosion resistance and conductivity to the separator base material made of stainless steel by performing surface treatment or the like.

As a surface treatment method for a separator base material containing a stainless steel base material, Patent Document 1 uses a vapor deposition method such as sputtering or a wet coating method such as spray injection to form a metal oxide film as an electrically conductive corrosion prevention coating film. It is described that a film is formed. Further, in Patent Document 2, deterioration of the stainless steel base material is suppressed by applying a raw material solution containing metal oxide fine particles on a stainless steel base material containing Cr by an anionic electrodeposition coating method and then firing the material. It is described to form a protective film for the purpose.

However, when the metal oxide film was directly formed on the stainless steel substrate by the method described in Patent Document 1, the adhesion between the metal oxide film and the substrate was not sufficiently obtained. Further, even when a metal layer for increasing the adhesive strength is further provided between the metal oxide film and the base material in order to improve the adhesion between the metal oxide film and the base material, sufficient adhesion and corrosion resistance can be obtained. It was difficult to obtain, and it was not practical enough as a separator for a fuel cell. Further, in the method described in Patent Document 2, a washing step for reducing the residual of pinholes and air bubbles in the protective film is indispensable, and a firing step for burning off the resin component in the coating film, and finally. There is a problem that the process becomes complicated, for example, it is necessary to carry out a sintering process for forming a protective film. Further, when the protective film is formed by the method described in Patent Document 2, uniform and sufficient strength, corrosion resistance and good conductivity are obtained over the entire surface of the base material due to the influence of pores remaining in the protective film. It was not obtained and was not fully satisfactory.

Therefore, there has been a long-awaited need for a laminated structure that is easy and easy to use, industrially advantageous, has good adhesion to a base material, and has excellent conductivity.

Japanese Unexamined Patent Publication No. 2006-156386 Japanese Unexamined Patent Publication No. 2014-067941

It is an object of the present invention to provide a laminated structure in which the functional expression of crystals is promoted, which is industrially advantageous.

As a result of diligent studies to achieve the above object, the present inventors have obtained a high crystallinity layer containing a conductive crystal containing a metal as a main component and a low crystallinity layer having a lower crystallinity than the high crystallinity layer. When at least one layer is alternately laminated to produce a crystalline laminated structure, the thickness of both the high crystalline layer and the low crystalline layer is 1 μm or less, and the high crystalline layer is a low crystalline layer. It was found that a crystalline laminated structure that is thicker and has the same main components of the high crystalline layer and the low crystalline layer promotes the functional expression of the high crystalline layer, and is particularly for fuel cells. We have found that it is very useful as a separator, and found that such a crystalline laminated structure can solve the above-mentioned conventional problems at once.
In addition, after obtaining the above findings, the present inventors have further studied and completed the present invention.

That is, the present invention relates to the following invention.
[1] A crystalline laminated structure in which at least one layer of a high crystalline layer containing a crystal containing a metal as a main component and a low crystalline layer having a lower crystalline property than the high crystalline layer are alternately laminated. The thickness of both the high crystalline layer and the low crystalline layer is 1 μm or less, the high crystalline layer is thicker than the low crystalline layer, and the main components of the high crystalline layer and the low crystalline layer are A crystalline laminated structure characterized by being the same .
[2] The crystalline laminated structure according to the above [1], wherein the thickness of the high crystalline layer is at least twice the thickness of the low crystalline layer.
[3] The crystalline laminated structure according to the above [1] or [2], wherein the highly crystalline layer has conductivity.
[4] The crystalline laminated structure according to any one of the above [1] to [3], wherein the crystal containing a metal is a crystalline metal oxide.
[5] The crystalline laminated structure according to the above [4], which is doped with a crystalline metal oxide.
[6] The crystalline laminated structure according to the above [4] or [5], wherein the crystalline metal oxide contains tin.
[7] The crystalline laminated structure according to any one of the above [1] to [6], wherein the thickness of both the high crystalline layer and the low crystalline layer is 0.1 μm or less .
[8] The crystalline laminated structure according to any one of the above [1] to [7], wherein both the high crystalline layer and the low crystalline layer have a thickness of 50 nm or less .
[9] The crystalline laminated structure according to any one of the above [1] to [8], wherein a low crystalline layer is formed on the substrate .
[10] The crystalline laminated structure according to the above [9], wherein the substrate is a conductive substrate .
[11] An electronic component including a conductive substrate, wherein the conductive substrate is the crystalline laminated structure according to any one of [1] to [10].
[12] An electronic device including an electronic component, wherein the electronic component is the electronic component according to the above [11].
[13] An electronic / electrical product on which an electronic device is mounted, wherein the electronic device is the electronic device according to the above [12].
[14] An information processing system including at least an electronic / electrical product and a CPU, wherein the electronic / electrical product is an electronic / electrical component according to the above [13].

According to the crystalline laminated structure of the present invention, it is possible to easily and easily promote the functional expression of crystals in an industrially advantageous manner.

It is a schematic block diagram of the film forming apparatus (mist CVD) used in this Example. It is a schematic block diagram of the separator made of the SUS substrate used in this invention. It is a figure which shows typically the cross section of the separator made of the SUS substrate used in this invention. It is a figure which shows the film formation condition and the XRD measurement result of this Example.

In the crystalline laminated structure of the present invention, at least one layer of a high crystalline layer containing a crystal containing a metal as a main component and a low crystalline layer having a lower crystallinity than the high crystalline layer are alternately laminated one by one. In the crystalline laminated structure, the thickness of both the high crystalline layer and the low crystalline layer is 1 μm or less, the high crystalline layer is thicker than the low crystalline layer, and the high crystalline layer and the low crystalline layer are low . It is characterized in that the main components of the crystalline layer are the same .

The high crystallinity layer can be confirmed to have crystallinity, and is not particularly limited as long as it has higher crystallinity than the low crystallinity layer. The crystallinity can be confirmed by the presence or absence of a peak in the XRD data obtained by using the X-ray diffractometer. Further, whether or not the crystallinity is higher than that of the low crystallinity layer can be confirmed by checking whether or not the peak of the XRD data is steeper than the peak of the XRD data of the low crystallinity layer. In the present invention, whether or not the product is steep can be determined by whether or not the half width is low. That is, the high crystalline layer usually has a value having a lower half width than the low crystalline layer. In the present invention, it is preferable that the thickness of the high crystalline layer is at least twice the thickness of the low crystalline layer because the functional promotion of the crystal is better.

Further, the highly crystalline layer preferably has conductivity. The crystal containing a metal, which is the main component of the high crystalline layer, may be a single crystal or a polycrystal, but is preferably a crystalline metal oxide, and more preferably doped with the crystalline metal oxide. preferable. In addition, it is preferable that the crystalline metal oxide contains tin because the development of conductivity is promoted more effectively. The "main component" is, for example, preferably 50% or more, more preferably 70% or more, still more preferably 90% or more of the crystals containing a metal among the components constituting the highly crystalline layer in terms of atomic ratio. It means that it is included, and may be 100%.

The low crystalline layer may be the same as the above high crystalline layer except for the crystallinity, and the main component is preferably a metal oxide, and more preferably tin. Further, in the present invention, the main components of the high crystallinity layer and the low crystallinity layer are the same . The thickness of the high crystallinity layer and the low crystallinity layer is not particularly limited, but both are preferably 0.1 μm or less, and more preferably 50 nm or less.
Further, in the present invention, it is preferable that the low crystalline layer is formed on the substrate because damage to the substrate can usually be reduced. The substrate is preferably a conductive substrate, and it is more preferable that a part or all of the surface of the substrate contains copper or an alloy thereof, aluminum or an alloy thereof, magnesium or an alloy thereof, or stainless steel as a main component. preferable.

Hereinafter, a preferred embodiment of the laminating method in the case of using a preferable substrate in the present invention will be described.
The mist or droplets (atomization / droplet atomization step) generated by atomizing or dropletizing the raw material solution containing metal are conveyed to the substrate by the carrier gas (transportation step), and then the substrate is subjected to the transfer. A conductive metal oxide film is formed on the substrate by thermally reacting the mist or droplets (depositioning step).

(Raw material solution)
The raw material solution is not particularly limited as long as it contains a metal and is capable of atomization or droplet formation, and may contain an inorganic material or an organic material. The metal may be a simple substance of a metal or a metal compound, and is not particularly limited as long as the object of the present invention is not impaired. In the present invention, the metal is preferably a metal having the third to fifth periods of the periodic table, and more preferably a metal having the fourth or fifth period of the periodic table. Examples of the metal in the third period of the periodic table include one or more metals selected from magnesium (Mg), aluminum (Al), silicon (Si), and phosphorus (P). Examples of the metal of the 4th period of the periodic table include titanium (Ti), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), and zinc ( One or more metals selected from Zn) and gallium (Ga) can be mentioned. Examples of the metal of the fifth period of the periodic table include zirconium (Zr), niobium (Nb), molybdenum (Mo), ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), and indium (Ag). One kind or two or more kinds of metals selected from In) and tin (Sn) and the like can be mentioned. In the present invention, the metal is preferably one or more metals selected from the group consisting of tin, zinc and chromium. The content of the metal in the raw material solution is not particularly limited, but is preferably 0.001% by weight to 80% by weight, and more preferably 0.01% by weight to 80% by weight.

In the present invention, as the raw material solution, a solution in which the metal is dissolved or dispersed in an organic solvent or water in the form of a complex or a salt can be preferably used. Examples of the form of the complex include an acetylacetonate complex, a carbonyl complex, an ammine complex, and a hydride complex. Examples of the salt form include organic metal salts (for example, metal acetate, metal oxalate, metal citrate, etc.), metal sulfide salts, nitrified metal salts, phosphorylated metal salts, and halogenated metal salts (for example, metal chloride). Salts, metal bromide salts, metal iodide salts, etc.) and the like.

The solvent of the raw material solution is not particularly limited, and may be an inorganic solvent such as water, an organic solvent such as alcohol, or a mixed solvent of an inorganic solvent and an organic solvent. In the present invention, the solvent preferably contains water, more preferably water or a mixed solvent of water and alcohol, and most preferably water. More specific examples of the water include pure water, ultrapure water, tap water, well water, mineral spring water, mineral water, hot spring water, spring water, fresh water, seawater, and the like. Ultrapure water is preferred.

Further, an additive such as a hydrohalic acid or an oxidizing agent may be mixed with the raw material solution. Examples of the hydrohalogen acid include hydrogen bromide, hydrochloric acid, and hydroiodide, and among them, hydrobromic acid or hydroiodide is preferable. Examples of the oxidizing agent include hydrogen peroxide (H ₂ O ₂ ), sodium peroxide (Na ₂ O ₂ ), barium peroxide (BaO ₂ ), benzoyl peroxide (C ₆ H ₅ CO) ₂ O ₂ and the like. Peroxides, hypochlorous acid (HClO), perchloric acid, nitric acid, ozone water, organic peroxides such as peracetic acid and nitrobenzene can be mentioned.

It is also preferable that the raw material solution contains a dopant. By including the dopant in the raw material solution, the conductivity of the obtained film can be controlled without ion implantation or the like, and the conductivity can be suitably imparted to the substrate. The dopant is not particularly limited as long as it does not interfere with the object of the present invention. Examples of the dopant include tin, germanium, silicon, titanium, zirconium, vanadium, niobium, antimony, tantalum, fluorine, chlorine, cerium and the like. The concentration of the dopant may be usually about 1 × 10 ¹⁶ / cm ³ to 1 × 10 ²² / cm ³ , and the concentration of the dopant may be as low as about 1 × 10 ¹⁷ / cm ³ or less, for example. You may. Further, according to the present invention, the dopant may be contained in a high concentration of about 1 × 10 ²⁰ / cm ³ or more.

(Hypokeimenon)
A part or all of the surface of the substrate contains copper or an alloy thereof, aluminum or an alloy thereof, magnesium or an alloy thereof or stainless steel as a main component, and a substrate capable of supporting the film is preferable. It is more preferable that a part or all of the substrate contains stainless steel as a main component, it is even more preferable that the entire surface of the substrate contains stainless steel as a main component, and the substrate contains stainless steel as a main component. Is the most preferable. Here, the main component is, for example, when a part or all of the surface of the substrate contains stainless steel as the main component, the stainless steel is contained in a component constituting a part or all of the surface of the substrate in atomic ratio. It means that the content is preferably 50% or more, more preferably 70% or more, still more preferably 90% or more, and may be 100%. The stainless steel is not particularly limited and may be a known stainless steel as long as the object of the present invention is not impaired. Examples of the stainless steel include ferritic stainless steel, martensitic stainless steel, austenite stainless steel and the like. Examples of ferritic stainless steels include SUS430, SUS434, and SUS405. Examples of martensitic stainless steel include SUS403, SUS410, and SUS431. Examples of the austenitic stainless steel include SUS201, SUS304, SUS304L, SUS304LN, SUS310S, SUS316, SUS316L, SUS317J1, SUS317J2, SUS321, SUS329J1, SUS836, SUSXM7 and the like specified in JIS. In the present invention, the stainless steel is preferably austenitic stainless steel.

The shape of the substrate may be any shape and is effective for any shape, for example, plate-like, fibrous, rod-like, columnar, prismatic, such as a flat plate or a disk. Examples thereof include a tubular shape, a spiral shape, a spherical shape, and a ring shape. In the present invention, a plate shape is preferable, the substrate is a plate shape, and the film formation is performed on both sides of the substrate. Is also preferable. Further, in the present invention, it is preferable that the substrate has an uneven shape on a part or all of the surface. In the present invention, it is possible to form a film uniformly and with good adhesion even on such a substrate having an uneven shape on a part or all of the surface. In the present invention, it is also preferable that the substrate is a separator.

(Uneven shape)
The uneven shape is not particularly limited as long as it is composed of a convex portion or a concave portion, and may be an uneven shape composed of a convex portion, an uneven shape composed of a convex portion, or a convex portion and a concave portion. It may have an uneven shape consisting of. Further, the uneven shape may be formed from regular convex portions or concave portions, or may be formed from irregular convex portions or concave portions. In the present invention, it is preferable that the uneven shape is formed periodically, and it is more preferable that the uneven shape forms a periodic and regular pattern. Further, in the present invention, it is preferable that the uneven shape forms a flow path pattern because the substrate after film formation can be suitably used as, for example, a separator for a fuel cell. The periodic and regular pattern of the uneven shape is not particularly limited, and examples thereof include a stripe shape, a dot shape, a grid shape, a mesh shape, and the like. In the present invention, the striped shape, the dot shape, or the grid shape is used. The shape is preferable. The flow path pattern is not particularly limited as long as it is a pattern that functions as a flow path for a liquid or gas when the substrate is applied as a separator for a fuel cell by using a known means, and the flow path is known. It may be a road pattern. Examples of the flow path pattern include a serpentine-type flow path pattern in which one or more flow paths are provided in a meandering manner, a parallel-type flow path pattern in which a plurality of linear flow paths are provided in parallel, and the like. Alternatively, a flow path pattern in which a serpentine type and a parallel type are combined can be mentioned. In the present invention, it is preferable that the flow path pattern is a parallel type flow path pattern. The cross-sectional shape of the convex or concave portion of the uneven shape is not particularly limited, but is, for example, U-shaped, U-shaped, inverted U-shaped, corrugated, or triangular or quadrangular (for example, square, rectangular or trapezoidal). ), Polygons such as pentagons or hexagons, etc. In addition, examples of the planar shape of the convex or concave portion of the uneven shape include a circle, an ellipse, a triangle, a quadrangle (for example, a square, a rectangle, a trapezoid, etc.), a polygon such as a pentagon or a hexagon, and the like. In the above, it is preferable that the planar shape is a rectangular shape.

The constituent material of the convex portion is not particularly limited and may be a known material. It may be an insulator material, a conductor material, a semiconductor material, or the substrate. Further, the constituent material may be amorphous, single crystal, or polycrystal. Examples of the constituent material of the convex portion include oxides such as Si, Ge, Ti, Zr, Hf, Ta, Sn, nitrides or carbides, carbines, diamonds, metals, and mixtures thereof. More specifically, a Si-containing compound containing SiO ₂ , SiN or polycrystalline silicon as a main component, and a metal having a melting point higher than the crystal growth temperature of the crystalline semiconductor (for example, platinum, gold, silver, palladium, rhodium). , Iridium, precious metals such as ruthenium, etc.). The content of the constituent material is preferably 50% or more, more preferably 70% or more, and most preferably 90% or more in the convex portion in terms of composition ratio. In the present invention, it is also preferable that the convex portion is made of a mask material that can be removed after the film formation. The means for removing the mask material is not particularly limited and may be a known means. Examples of the removing means include dry etching and wet etching.

The means for forming the convex portion may be a known means, for example, known patterning processing such as photolithography, electron beam lithography, laser patterning, screen printing, and subsequent etching (for example, dry etching or wet etching). Means and the like can be mentioned. In the present invention, the convex portion is preferably striped, meshed or latticed, and more preferably latticed. It is also preferable that the convex portion is a convex portion provided by processing the substrate. The processing means is not particularly limited and may be a known processing means. Examples of the processing means include etching (for example, dry etching or wet etching), press processing, and the like.

The concave portion is not particularly limited, but may be the same as the constituent material of the convex portion, or may be the substrate. In the present invention, the recesses are preferably striped, meshed or latticed. As the means for forming the concave portion, the same means as the means for forming the convex portion can be used. It is also preferable that the recess is a recess provided by the mask material. Further, it is also preferable that the recess is a recess provided by processing the substrate. The processing means may be a known groove processing means. The width of the recess, the depth of the groove, the width of the terrace, and the like are not particularly limited as long as the object of the present invention is not impaired, and can be appropriately set.
A schematic configuration diagram of a separator made of a SUS substrate suitable for the present invention is shown in FIG. The separator preferably used in the present invention is a separator having a parallel flow path pattern, and is formed on the SUS base material 13 by screen printing, and the flow path forming layer 14 for forming the flow path pattern and the flow path forming layer 14 and the like. The flow path wall 15 and the manifold 16 for supplying the reaction gas and the refrigerant to each single cell are provided. A diagram schematically showing a cross section of a separator preferably used in the present invention is shown in FIG.

(Atomization / droplet formation process)
In the atomization / droplet atomization step, the raw material solution is prepared, and the raw material solution is atomized to generate mist or droplets. The atomizing means is not particularly limited as long as the raw material solution can be atomized, and may be a known atomizing means, but in the present invention, the atomizing means using ultrasonic waves is preferable. The mist preferably has an initial velocity of zero and floats in the air, and more preferably a mist that floats in space and can be conveyed as a gas instead of being sprayed like a spray. The droplet size of the mist is not particularly limited and may be a droplet of about several mm, but is preferably 50 μm or less, and more preferably 1 to 10 μm.

(Transport process)
In the transfer step, the mist or droplets generated in the atomization / droplet atomization step are conveyed to the substrate with a carrier gas. The type of carrier gas is not particularly limited as long as the object of the present invention is not impaired, and for example, an inert gas such as oxygen, ozone, nitrogen or argon, or a reducing gas such as hydrogen gas or forming gas is a suitable example. Is mentioned as. In the present invention, the carrier gas is more preferably oxygen or an inert gas. Further, the type of the carrier gas may be one type, but may be two or more types, and a diluted gas having a changed carrier gas concentration (for example, a 10-fold diluted gas or the like) may be used as the second carrier gas. Further may be used. Further, the carrier gas may be supplied not only at one place but also at two or more places. The flow rate of the carrier gas is not particularly limited, but is preferably 0.01 to 20 L / min, and more preferably 1 to 10 L / min. In the case of the diluted gas, the flow rate of the diluted gas is preferably 0.001 to 10 L / min, more preferably 0.1 to 5 L / min.

(Film formation process)
In the film forming step, the mist or the droplets are thermally reacted to form a film on the substrate. The thermal reaction may be any effect as long as the mist reacts with heat, and the reaction conditions and the like are not particularly limited as long as the object of the present invention is not impaired. In this step, the thermal reaction is usually carried out at a temperature equal to or higher than the evaporation temperature of the solvent, but is preferably not too high (for example, 800 ° C.) or lower, more preferably 600 ° C. or lower, and most preferably 500 ° C. or lower. .. Further, the thermal reaction may be carried out under any atmosphere of vacuum, non-oxygen atmosphere, reducing gas atmosphere and oxygen atmosphere, and under any conditions of atmospheric pressure, pressurization and decompression. However, in the present invention, it is preferably performed under atmospheric pressure.

As described above, the crystalline laminated structure of the present invention can be obtained by laminating and changing the film forming conditions. The film thickness of the obtained film can be easily adjusted by adjusting the film formation time.

Further, according to the above-mentioned film forming method, it is a conductive laminated structure in which a conductive metal oxide film is formed directly on the substrate or via another layer, and the film thickness of the conductive metal oxide film is formed. It is possible to obtain a conductive laminated structure having a contact resistance of 30 nm or more and a contact resistance of 100 mΩcm ² or less. Further, according to the above-mentioned preferable film-forming method, the conductive laminated structure having a contact resistance of 50 mΩcm ² or less can be obtained, and according to further preferable film-forming conditions, the conductivity having a contact resistance of 20 mΩcm ² or less can be obtained. A laminated structure can be obtained.

Examples of the conductive laminated structure include various electronic parts such as a current collector, an electromagnetic wave shielding material, an electrode, a heat sink, a heat radiating component, an electronic component, a semiconductor component, and a separator for a fuel cell. The conductive laminated structure can be applied to an electronic device or the like including the various parts according to a conventional method. The electronic device is not particularly limited, but in the present invention, for example, a CPU-equipped electronic device such as a digital camera, a printer, a projector, a personal computer, or a mobile phone, a power supply unit-mounted electronic device such as a vacuum cleaner, an iron, or the like. Suitable examples include motors, drive mechanisms, electric vehicles, electric airplanes, small electric devices, drive electronic devices such as MEMS, and the like. Further, by using known means, the electronic device can be mounted on an electronic / electric product, and further, an information processing system can be constructed by combining with a CPU.

(Example 1)
1. 1. Film formation device The mist CVD device 1 used in this embodiment will be described with reference to FIG. The mist CVD device 1 includes a carrier gas source 2a for supplying a carrier gas, a flow control valve 3a for adjusting the flow rate of the carrier gas sent out from the carrier gas source 2a, and a carrier gas (diluted) for supplying the carrier gas (diluted). Diluted) source 2b, flow control valve 3b for adjusting the flow rate of carrier gas (diluted) sent out from the carrier gas (diluted) source 2b, mist generation source 4 containing the raw material solution 4a, and water 5a. In the container 5 to be put in, the ultrasonic transducer 6 attached to the bottom surface of the container 5, the film forming chamber 7, the supply pipe 9 connecting the mist generation source 4 to the film forming chamber 7, and the film forming chamber 7. It includes an installed hot plate 8 and an exhaust port 11 for exhausting mist, droplets, and exhaust gas after a thermal reaction. The substrate 10 is installed on the hot plate 8.

2. 2. Preparation of raw material solution An aqueous solution of tin chloride was used as the raw material solution.

3. 3. Preparation for film formation 2. The raw material solution 4a of the above was housed in the mist generation source 4. Next, as the substrate 10, a separator made of a SUS substrate having an uneven shape on the surface was placed on the hot plate 8 and the hot plate 8 was operated to raise the substrate temperature to 450 ° C. Next, the flow rate control valve 3a is opened, the carrier gas is supplied into the film forming chamber 7 from the carrier gas supply means 2a which is the carrier gas source, and the atmosphere of the film forming chamber 7 is sufficiently replaced with the carrier gas. The flow rate of the carrier gas was adjusted to 0.5 L / min, and the flow rate of the carrier gas (diluted) was adjusted to 4.5 L / min. Oxygen was used as the carrier gas.

4. Film formation Next, the ultrasonic transducer 6 was vibrated at 2.4 MHz, and the vibration was propagated to the raw material solution 4a through water 5a to atomize the raw material solution 4a to generate mist 4b. This mist 4b is introduced into the film forming chamber 7 by the carrier gas through the supply pipe 9, and the mist thermally reacts in the vicinity of the substrate 10 under the conditions shown in FIG. 4 under atmospheric pressure, and the substrate 10 A film was formed on top. The results of XRD are also shown in FIG.

5. evaluation
Above 4. Contrary to expectations, the crystalline laminated structure obtained in 1 was significantly superior to other conductive single-layer films and the like in terms of contact resistance and the like.

The present invention can be used in a wide variety of fields, and in particular, an electronic device including various parts such as a current collector, an electromagnetic wave shielding material, an electrode, a heat radiating plate, a heat radiating part, an electronic part, a semiconductor part, and a separator for a fuel cell. It is useful for.

1 Formation device 2a Carrier gas source 2b Carrier gas (dilution) source 3a Flow control valve 3b Flow control valve 4 Mist generation source 4a Raw material solution 4b Raw material fine particles 5 Container 5a Water 6 Ultrasonic transducer 7 Formation chamber 8 Hot plate 9 Supply pipe 10 Substrate 11 Exhaust port 12 Separator 13 SUS base material 14 Flow path wall 15 Manifold 16 Flow path forming layer

Claims (12)

A conductive laminate in which at least one layer of a high crystalline layer containing a crystal containing a metal as a main component and a low crystalline layer having a lower crystallinity than the high crystalline layer are alternately laminated on a conductive substrate. In the structure, the thickness of both the high crystalline layer and the low crystalline layer is 1 μm or less, the high crystalline layer is thicker than the low crystalline layer, and the main of the high crystalline layer and the low crystalline layer is A conductive laminated structure having the same components and characterized in that the crystal containing the metal is a crystalline metal oxide . The conductive laminated structure according to claim 1, wherein the thickness of the high crystalline layer is at least twice the thickness of the low crystalline layer. The conductive laminated structure according to claim 1 or 2, wherein the highly crystalline layer has conductivity. The conductive laminated structure according to any one of claims 1 to 3, wherein the crystalline metal oxide is doped. The conductive laminated structure according to any one of claims 1 to 4, wherein the crystalline metal oxide contains tin. The conductive laminated structure according to any one of claims 1 to 5 , wherein both the high crystalline layer and the low crystalline layer have a thickness of 0.1 μm or less. The conductive laminated structure according to any one of claims 1 to 6 , wherein both the high crystallinity layer and the low crystallinity layer have a thickness of 50 nm or less. The conductive laminated structure according to any one of claims 1 to 7, wherein a low crystalline layer is formed on the conductive substrate. An electronic component including a conductive substrate, wherein the conductive substrate is the conductive laminated structure according to any one of claims 1 to 8 . An electronic device including electronic components, wherein the electronic component is the electronic component according to claim 9 . An electronic / electrical product on which an electronic device is mounted, wherein the electronic device is the electronic device according to claim 10 . An information processing system including at least an electronic / electrical product and a CPU, wherein the electronic / electrical product is an electronic / electrical component according to claim 11 .

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