JP2006082020A - Chemical reaction apparatus and power supply system - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a chemical reaction device having a structure capable of realizing a better bonding state by a simple manufacturing process and capable of being further reduced in size and thickness, and a portable power supply system using the chemical reaction device. I will provide a.
A chemical reaction apparatus (microreactor) generally includes a main substrate 10 made of glass (SiO ₂ ) or the like in which a reaction channel 11 having a predetermined width and depth is formed on one side, and the main substrate 10. A sub-substrate 20 such as glass (SiO ₂ ) provided with a thin-film heater 30 having a predetermined planar shape on the other surface side is provided between the main substrate 10 and the sub-substrate 20. And a bonding film 21 formed by oxidizing a part of tantalum silicon (Ta _1-x Si _x ) having an amorphous material so as to be laminated to each other.
[Selection] Figure 1

Description

  The present invention relates to a chemical reaction apparatus and a power supply system, and in particular, a chemical reaction apparatus capable of generating a desired fluid substance by a reaction in a reaction channel formed on a micro substrate, and a power source to which the chemical reaction apparatus is applied. About the system.

Conventionally, in the field of chemical reaction engineering, a chemical reaction apparatus ("" that produces a desired fluid substance by a chemical reaction (catalytic reaction) of a fluidized mixed substance by a catalyst provided in a reaction channel (channel). Also known as “flow channel reactor” or “channel reactor”).
In recent years, a so-called micromachine manufacturing technology, in which microfabrication technology or the like accumulated in semiconductor device manufacturing technology such as integrated circuits has been introduced to the technical field of such chemical reaction apparatus, for example, a single silicon chip Research and development of microreactors (or “microchannel reactors”) in which various functional elements such as millimeter-order or micron-order mixers, reaction flow paths, and analyzers are integrated in the micro space above are actively conducted. Yes.

Here, a schematic configuration of the microreactor in the prior art will be briefly described with reference to the drawings.
FIG. 17 is a schematic configuration diagram showing a basic structure of a microreactor in the prior art.
As schematically shown in FIGS. 17A, 17B, and 17C, the microreactor is, for example, on the micron order by using a photoetching technique or the like on one side of a small main substrate 10p such as silicon (Si). A reaction channel (microchannel) 11p having a groove-like cross-sectional structure with a width and a depth and having a predetermined plane pattern (channel shape) is formed on one side of the main substrate 10p. It has a configuration in which a closed substrate 20p such as glass (SiO ₂ ) is joined so as to close the open portion of the reaction flow path 11p (the open end of the groove portion).

  In such a microreactor, when the chemical reaction (catalytic reaction) promoted in the reaction channel is accompanied by an endothermic catalytic reaction under a predetermined thermal condition, as shown in FIG. A catalyst layer 12p having a predetermined catalyst attached to the inner wall surface of the path 11p is formed, and a heating resistor for supplying predetermined heat energy to the reaction channel 11p (specifically, the catalyst layer 12p) during the chemical reaction. A configuration in which a thin film heater 30p made of, for example, is formed is applied. Here, as shown in FIGS. 17B and 17C, for example, the thin film heater 30p reacts with the above reaction on the other surface side of the closed substrate 20p (the surface on the side opposite to the bonding side with the main substrate 10p). It is formed so as to have a shape corresponding to the planar pattern (flow channel shape) of the flow channel 11p.

  Also, in FIGS. 17A and 17C, hatching is shown for convenience in order to clarify the shapes of the reaction flow path 10p and the thin film heater 30p. FIG. 17 shows a configuration in which the fluid substance introduction part 13p and the discharge part 14p to the reaction flow path 11p are provided on the side part of the chemical reaction apparatus (the side end face of the main board 10p). Even if it has a configuration in which the introduction portion 13p and the discharge portion 14p are provided in a direction perpendicular to 10p or the closed substrate 20p (that is, a direction perpendicular to the paper surface in FIGS. 17A and 17C). Good.

  Here, regarding the configuration of the microreactor as shown in FIG. 17, for example, in Patent Document 1 or the like, a groove portion serving as a flow path having a predetermined shape is formed on one surface side (bonding surface side) of one glass substrate. In addition, a configuration is described in which the upper glass substrate on the other side is stacked and bonded or heat-sealed so as to close the open portion of the groove.

  In addition, when the bondability and adhesion between the main substrate 10p and the closed substrate 20p are not good, the reaction characteristics deteriorate or malfunction due to leakage of the fluid substance flowing through the reaction flow path 11p, and contamination to peripheral equipment occurs. Because the thermal expansion of the substrate due to the thermal energy from the thin film heater 30p causes peeling of the bonding surface, damage to the substrate, and the like, it is necessary to apply a technique that can obtain a very good bonding state. Anodic bonding is considered to be effective as a bonding method that can meet such demands.

FIG. 18 is a conceptual diagram showing an anodic bonding method applied to a microreactor manufacturing process in the prior art. Here, the same components as those of the microreactor described above are denoted by the same reference numerals, and the reaction channel and the thin film heater are not shown.
As shown in FIG. 18 (a), for example, the substrate-to-substrate bonded structure by anodic bonding is formed on one side of the main substrate 10p made of silicon (Si) and a metal film for oxidation that is oxidized as a single body during anodic bonding. As a bonding metal film 15p formed by laminating a non-oxidizing metal film that is not oxidized during anodic bonding, a known vapor deposition method or sputtering method is formed, and then heat treatment is performed under a predetermined temperature condition so that both of the single metals are eutectic After the mixing, as shown in FIG. 18B, a closed substrate 20p such as glass (SiO ₂ ) is stacked on the bonding metal film 15p, and the bonding metal film 15p and the closing substrate are heated under a temperature condition of about several hundred degrees Celsius. By applying a DC voltage of about several hundred volts between 20p, the oxidizing metal distributed on the surface of the bonding metal film 15p is combined with oxygen molecules on the closed substrate (glass substrate) 20p, thereby realizing bonding with high bonding strength. Be done It is intended to refer.

Here, according to the principle of anodic bonding, a good bonding state can be obtained with a glass (SiO ₂ ) substrate that is a closed substrate. As a metal applied to the bonding metal film, for example, aluminum (Al) Although nickel (Ni) and the like are known, even when silicon (Si) that exhibits the same behavior as these metals is applied, a good bonding state with a glass substrate can be obtained. Are known. That is, as shown in FIG. 18C, the main substrate (silicon substrate) 10p made of silicon and the closed substrate (glass substrate) 20p made of glass are directly bonded by anodic bonding to obtain a good bonded state.

JP 2004-53545 A (Pages 5 to 6, FIGS. 1 to 4)

  As described above, in the microreactor in the prior art, in order to realize a good bonding state (bonding with high bonding strength) between the main substrate and the closed substrate, a bonding metal film is interposed between the main substrate and the closed substrate. An anodic bonding configuration, for example, a configuration in which a main substrate made of silicon and a closed substrate made of glass are directly anodic bonded are applied.

  However, in the structure in which the main substrate made of the silicon substrate and the closed substrate made of the glass substrate are directly anodic bonded among the bonding structures as described above, it is not necessary to form a bonding metal film, so that the manufacturing process is simplified. However, since the silicon substrate as the main substrate is very expensive, there is a problem that the manufacturing cost of the microreactor increases. This also applies to a configuration in which a bonding metal film made of a single metal is interposed between the main substrate and the closed substrate. When a silicon substrate is applied as the main substrate, there is a problem that the manufacturing cost increases. Was.

Therefore, in a configuration in which a bonding metal film is interposed between the main substrate and the closed substrate, for example, it is considered effective from the viewpoint of manufacturing cost to apply a glass substrate. Had problems as shown.
For example, when a bonding metal film is composed of an oxidation metal film that is oxidized during anodic bonding as a single body and a non-oxidation metal film that is not oxidized during anodic bonding as a single body, Bonded to a closed substrate (glass substrate) during anodic bonding by eutectic melting under temperature conditions and diffusing the metal film for oxidation into the non-oxidizing metal and distributing it on the surface of the bonding metal film as a eutectic mixture However, in the case of a eutectic mixture, since it is not uniformly dispersed at the atomic level, a domain group of simple metals composing the metal film for oxidation and a domain group of simple metals composing the non-oxidized metal are formed. End up. In this case, since a domain group of simple metals having a non-oxidized metal composition exists on the surface of the bonding metal film, an oxidation reaction does not occur due to oxygen atoms in the glass substrate, and a portion where bonding cannot be performed occurs. There was a problem that peeling or damage might occur.

  Therefore, in view of the above problems, the present invention has a structure capable of realizing a better bonding state with a simple manufacturing process, a chemical reaction device capable of further miniaturization and thinning, and the chemical reaction. An object is to provide a portable power supply system using the apparatus.

The invention according to claim 1 is a chemical reaction apparatus for generating a chemical reaction in a predetermined reaction channel.
at least,
A first substrate having a groove-like reaction channel formed on one side thereof;
A second substrate provided opposite to the first substrate and closing an open end of the reaction channel;
An amorphous bonding film interposed between the first substrate and the second substrate and bonded to an oxygen atom contained in one of the first substrate and the second substrate; It is characterized by having.

The bonding film is formed into a thin film by sputtering on the substrate on one side of the first insulating substrate and the second insulating substrate, and is anodic bonded to the substrate on the other side. May be joined.
In the bonding film, tantalum and silicon are preferably dissolved. With such a material, it is possible to prevent oxidation at a high temperature such as anodic bonding from proceeding excessively, so that the material does not become brittle due to excessive oxidation.

The bonding film is particularly preferably set to a composition ratio of silicon 0.3 with respect to tantalum 0.7.
The chemical reaction device has a configuration in which a predetermined catalytic material is attached to and formed on an inner wall surface of the reaction flow path, and the chemical reaction causes the first fluid material to be converted into the second fluid by the catalytic reaction with the catalytic material. It may be converted into a fluid substance.

  The chemical reaction device is a reaction device that generates a chemical reaction in which a first fluid substance is converted into a second fluid substance in a predetermined reaction channel, and a temperature adjustment layer is formed in a region corresponding to the reaction channel. The chemical reaction in the reaction channel may be promoted by thermal energy supplied from the temperature adjustment layer.

  In this case, the first fluid substance is a mixed gas containing a hydrocarbon-based gas and water vapor, the second fluid substance is hydrogen gas, and the chemical reaction device includes the reaction channel. The second fluid substance may be generated from the first fluid substance by generating a steam reforming reaction in the inside.

  The invention described in claim 6 includes a chemical reaction device for generating a chemical reaction for converting the first fluid substance into the second fluid substance in a predetermined reaction flow path, and the second reaction product generated by the chemical reaction device. The chemical reaction device includes at least a first insulating substrate made of a glass substrate having a groove-like reaction channel formed on one surface side thereof. An amorphous bonding film interposed between the first substrate and the second substrate and bonded to oxygen atoms contained in one of the first substrate and the second substrate; The reaction part which consists of these is provided, It is characterized by the above-mentioned.

  In the power supply system, the bonding film includes a bonding metal film formed by sputtering on one of the first substrate and the second substrate, and the first substrate and the second substrate by anodic bonding. The first substrate and the second substrate may be bonded together with the other oxygen atom of the second substrate.

In the power supply system, the bonding film is preferably made of a compound of tantalum and silicon.
In the system, the bonding film is particularly preferably set to a composition ratio of silicon 0.3 with respect to tantalum 0.7.

In the power supply system, the chemical reaction device has a configuration in which a predetermined catalytic substance is attached and formed on an inner wall surface of the reaction channel, and a temperature adjustment layer is formed in a region corresponding to the reaction channel. You may have.
In the power supply system, the chemical reaction device may have a configuration in which a plurality of the reaction parts are stacked, and each reaction part may cause a different chemical reaction.
In the power supply system, the chemical reaction device may generate hydrogen gas from hydrocarbon-based liquid fuel and water by causing different chemical reactions in the plurality of reaction units.

In the power supply system, any one of the plurality of reaction units constituting the chemical reaction device causes a vaporization reaction in the reaction flow path, whereby a hydrocarbon-based liquid fuel and water are generated. From the above, the hydrocarbon-based gas and water vapor may be generated.
In the power supply system, any one of the plurality of reaction units constituting the chemical reaction device may generate a hydrocarbon reforming reaction in the reaction flow path to generate a hydrocarbon-based gas. Hydrogen gas may be generated from water vapor.

In the power supply system, any one of the plurality of reaction units constituting the chemical reaction device causes an aqueous shift reaction and a selective oxidation reaction in the reaction flow path, thereby producing carbon monoxide. Hydrogen gas and carbon dioxide may be generated from a mixed gas containing gas and oxygen.
In the power supply system, any one of the plurality of reaction units constituting the chemical reaction device causes the other reaction unit to generate a combustion reaction of hydrogen gas in the reaction channel. Thermal energy for promoting the chemical reaction in may be generated.

  According to the present invention, since the crystallinity is relatively low due to the amorphous nature of the bonding film, generation of crystal grain boundaries inside the film is suppressed, and oxidation does not proceed excessively in the thickness direction. When bonded to oxygen atoms contained in one of the substrate and the second substrate, it does not become brittle and bonds well and a good bonding state between the first substrate and the second substrate can be obtained.

Embodiments of a chemical reaction apparatus according to the present invention and a power supply system to which the chemical reaction apparatus is applied will be described below with reference to the drawings.
<Chemical reactor>
First, a chemical reaction apparatus according to the present invention will be described with reference to the drawings.
FIG. 1 is a schematic view showing an embodiment of a chemical reaction device and a manufacturing process thereof according to the present invention, and FIG. 2 is a plan view (flow pattern) of a reaction channel applied to the chemical reaction device according to this embodiment. It is the schematic which shows an example of a road shape. In FIG. 2, in order to clarify the shape of the reaction channel, it is hatched for convenience.

A chemical reaction apparatus (microreactor) according to the present invention generally has a groove-like cross-sectional structure having a predetermined width and depth on one surface as shown in FIG. A main substrate (first substrate) 10 such as glass (SiO ₂ ) in which a reaction channel 11 having a channel shape) is formed, and is provided to face one surface side of the main substrate 10, and the other surface side A sub-substrate (second substrate) 20 such as glass (SiO ₂ ) on which a thin film heater (temperature adjustment layer) 30 having a predetermined planar shape is formed, and the main substrate 10 and the sub-substrate 20 are interposed. The provided bonding film 21 is bonded to each other so as to be laminated.

  Here, the planar pattern (flow channel shape) of the reaction flow channel 11 formed on the main substrate 10 is, for example, as shown in FIG. On the other hand, it may have a meandering shape, or may have a relatively wide reaction chamber 15 in the middle of the flow path, as shown in FIG. In short, what is necessary is just to have an appropriate shape according to the type and characteristics of the chemical reaction executed in the chemical reaction apparatus.

  2 shows a configuration in which the introduction part 13 and the discharge part 14 of the fluid substance to the reaction flow path 11 are provided on the side end surface of the main substrate 10, but the present invention is not limited to this. The introduction unit 13 and the discharge unit 14 may be provided in a direction perpendicular to the substrate surface (that is, a direction perpendicular to the paper surface in FIG. 2).

  Further, on the inner wall surface of the reaction channel 11, for example, a catalyst layer 12 for promoting a chemical reaction (catalytic reaction) in the reaction channel 11 is formed, and the other surface side ( The thin film heater 30 provided on the surface opposite to the surface facing the main substrate) is, for example, a planar pattern (channel shape) of the reaction channel 11 as in the configuration shown in FIG. It has the shape corresponding to. The thin film heater 30 is not limited to the configuration formed on the other surface side of the sub-substrate 20, and may be formed on the other surface side of the main substrate 10, for example. It is not limited to a shape (for example, a meandering shape corresponding to FIG. 2 (a)) that substantially matches the planar pattern (flow channel shape) of the channel 11. It may have a rectangular shape.

  In addition, in the configuration shown in FIG. 1A, at least the glass substrate constituting the sub-substrate 20 has a plate thickness of 0.2 mm or less, for example, and is joined between the main substrate 10 and the sub-substrate 20. The film 21 is constituted by a film in which at least a part of an amorphous alloy film 21 a having a film thickness of, for example, about several hundred nm (several thousand thousand) is bonded to oxygen atoms in the sub-substrate 20.

This bonding film has a plurality of single metals that can be covalently bonded to oxygen atoms during anodic bonding, and an amorphous alloy film 21a in which these single metals have an amorphous structure (see FIG. 1B). Is a film at least oxidized by anodic bonding. Since the plurality of simple metals in the state of the bonding film 21 are all bonded to oxygen atoms contained in the glass in the main substrate 10, the main substrate 10 and the sub-substrate 20 can be bonded well. In particular, in the present invention, a metal compound (tantalum silicon Ta _1-x Si _x ; x = 0.3) composed of tantalum and silicon having a specific composition ratio may be favorably applied as the amorphous alloy film. it can. The specific configuration (material, film quality, etc.) of the bonding film according to the present invention will be verified in detail later.

As shown schematically in FIG. 1B, the manufacturing process of the chemical reaction device having such a configuration is first performed on one surface side of the main substrate 10 made of glass (SiO ₂ ) using a photoetching technique or the like. For example, a groove 11a having a cross-sectional shape with a width and depth on the order of microns is formed, and aluminum is coated on the groove 11a, and then anodized to form a porous film made of aluminum oxide. Thereafter, the catalyst layer 12 having catalyst particles supported on the inner wall surface of the porous film of the groove 11a is formed by immersing in a suspension of a copper-zinc (Cu-Zn) catalyst material and annealing.

Independently of the step of forming the groove 11a on the main substrate 10 side, for example, tantalum atoms and silicon (silicon) atoms are formed on one side of the sub-substrate 20 made of glass (SiO ₂ ) having a thickness of 0.2 mm or less. Tantalum having an amorphous structure with a thickness of at least several hundreds of nanometers by RF sputtering (sputtering method) using a target arranged in a stripe pattern at a predetermined ratio (a ratio of silicon 3 to tantalum 7 in the present invention) An amorphous alloy film 21a including a silicon (TaSi) thin film is formed by a single process. The thickness of the amorphous alloy film 21a is about 200 nm to 500 nm, which is suitable for anodic bonding. However, if the film is deposited too thick, wrinkles occur and the film thickness becomes non-uniform. Thickness is preferred. Then, a thin film heater 30 made of a heating resistor containing gold (Au) or the like is formed on the other surface side of the sub substrate 20, for example.

  Next, the one surface side of the main substrate 10 and the amorphous alloy film 21a formed on the one surface side of the sub substrate 20 are overlapped so as to face each other, and as shown in FIG. A DC voltage of 300 V to 2000 V is applied between the main substrate 10 and the amorphous alloy film 21a under a temperature condition of ° C., and both tantalum atoms and silicon atoms of the amorphous alloy film 21a are mainly formed by anodic bonding. The main substrate 10 and the sub-substrate 20 are bonded together by combining with oxygen atoms, which are glass components of the substrate 10, to form a bonding film 21. Thereby, the open end of the groove 11a formed in the main substrate is closed by the sub-substrate and the bonding film 21, and the reaction channel 11 having a predetermined channel shape is formed.

  Here, in FIG. 1B, the process of forming the amorphous alloy film 21a by the sputtering method on the sub-substrate side is shown, but the present invention is not limited to this. After forming the amorphous alloy film 21a on the one surface side of the substrate 10, the groove 11a may be formed, and the sub-substrate 20 may be bonded to the amorphous alloy film 21a to close the groove 11a. Further, for example, after the thin film heater 30 is formed on the other surface side of the sub-substrate 20, the anodic bonding may be performed after the amorphous alloy film 21a is formed on one surface side.

  In the chemical reaction apparatus having such a configuration, for example, a mixed fluid (mixed gas; first fluid substance) obtained by vaporizing a raw material material composed of methanol and water is introduced into the reaction flow path 11 and is not illustrated. By applying a predetermined voltage to the thin-film heater 30 by the heater power source heated and supplying predetermined heat energy to the catalyst layer 12 adhered and formed in the reaction channel 11, an endothermic catalytic reaction (methanol steam reforming) Reaction) occurs to generate hydrogen gas (second fluid substance) and a small amount of carbon dioxide. The technology to generate hydrogen gas from hydrocarbon (or alcohol) raw materials such as methanol by catalytic reaction is a fuel reformer in fuel cell systems that has been remarkably researched and developed for full-scale practical use in recent years. This technique is also applied to the apparatus, and an application example of the chemical reaction apparatus according to the present invention to the fuel cell system will be described in detail later.

Next, the material and characteristics of the amorphous alloy film 21a that becomes the bonding film 21 applied to the chemical reaction apparatus having the above-described configuration will be described in detail.
The inventors of the present application conducted various experiments on a plurality of metal materials (metallic materials) applicable to the amorphous alloy film 21a to be the bonding film 21 applied to the chemical reaction apparatus according to the present invention. When the effectiveness was verified, as described above, it was found that an amorphous alloy composed of a metal compound of tantalum and silicon (Ta _1-x Si _x ) exhibits extremely good characteristics. The reason will be specifically described below.

FIG. 3 is a schematic view showing a model structure used for verifying the characteristics of a metal material (metallic material) applicable to the amorphous alloy film according to the present embodiment.
The inventors of the present application use a model structure similar to the chemical reaction apparatus having the configuration shown in FIG. 1 using various metal materials (metallic materials) applicable to the amorphous alloy film. The quality of the characteristics was judged. Here, in order to verify the characteristics as an amorphous alloy film, a metal thin film having a thickness of several hundred nm was formed on one surface side of a glass substrate by a sputtering method, and the film quality was examined.

Specifically, as the model structure, as shown in FIGS. 3A and 3B, a buffer film PRT which is a compound film (Ta—Si—O) made of tantalum, silicon, and oxygen on a glass substrate SUB. For example, a tantalum (Ta) thin film, or a bonding metal film LY (Ta) made of tantalum silicon (Ta _1-x Si _x ) according to the present invention, an amorphous alloy film The verification was performed using a configuration in which LY (TaSi) was formed to have a thickness of, for example, 200 nm. Here, tantalum (Ta) is a metal material which is oxidized during anodic bonding, which is generally applied as a simple substance, and similarly, silicon (Si) is oxidized as a simple substance, during anodic bonding which is generally applied. Metal material. In addition, the buffer film PRT, which is a compound film (Ta—Si—O) made of tantalum, silicon, and oxygen formed on a glass substrate (for example, a closed substrate) is applied to an actual chemical reaction apparatus. It is a protective film for preventing the alkali ions contained in the glass substrate from being deposited during anodic bonding.

  FIG. 4 is a diagram showing a composition ratio immediately after the formation of a tantalum film having a thickness of 200 nm on a (Ta—Si—O) buffer film PRT coated on a substrate as a comparative example, and FIG. It is a figure which shows the composition ratio after heat-processing the tantalum single-piece | unit film | membrane of FIG. 4 in the temperature range at the time of anodic bonding. FIG. 6 is data showing the results of X-ray diffraction measurement for verifying the crystallinity of the tantalum film formed on the substrate shown in FIG.

  First, in the model structure (FIG. 3A) in which a buffer film PRT made of tantalum, silicon, and oxygen and a bonding metal film LY (Ta) made of tantalum (Ta) are stacked on a glass substrate SUB. Immediately after that, as shown in FIG. 4, since tantalum has a characteristic that it is relatively easily oxidized by oxygen in the atmosphere, the composition ratio of oxygen (contained in the very surface layer of the bonding metal film LY (Ta)). Although the amount was high, a composition containing only tantalum was shown over the entire region up to a depth (film thickness) of 200 nm from the film surface, which is a boundary with the buffer film PRT. In a region where the depth from the film surface is deeper than 200 nm, the predetermined composition ratio (molar ratio) of tantalum, silicon, and oxygen constituting the buffer film PRT that is the protective film is approximately tantalum 0.2, silicon 0. 0.1, oxygen 0.7.

  Next, after this model structure is subjected to a heat treatment in which a temperature of 400 ° C. is continuously applied for 30 minutes in the air, as shown in FIG. It was found that the composition ratio of oxygen increased almost throughout the region, and oxidation by oxygen in the atmosphere progressed.

For example, when the crystallinity of a tantalum film formed with a film thickness of several hundreds of nanometers on a silicon substrate by using a sputtering method is measured using an X-ray diffractometer, as shown in FIG. A tantalum thin film formed on the substrate has a sharp peak indicating a very narrow intensity and a very high intensity (approximately 12000 CPS) at about 33 to 34 deg. It has an extremely high film quality (single crystallinity), and as a result, a crystal grain boundary is generated inside the film, and oxygen enters the grain boundary by the heat treatment in the atmosphere as described above, and covers the entire tantalum film. It is thought that oxidation progressed.
When oxidation progresses over the entire area of such a metal film made of tantalum alone, the film quality becomes brittle, the bonding state deteriorates, and there is a problem that the bonding strength is insufficient and the substrate is peeled off or damaged.

  FIG. 7 shows the composition ratio immediately after film formation when amorphous tantalum silicon having a thickness of 200 nm is applied to the amorphous alloy film on the (Ta—Si—O) buffer film PRT coated on the substrate. FIG. 8 is a diagram showing the composition ratio after the amorphous alloy film of tantalum silicon in FIG. 7 is heat-treated in the temperature range during anodic bonding. FIG. 9 is data showing the results of X-ray diffraction measurement for verifying the crystallinity of the tantalum silicon film formed on the silicon substrate. FIG. 10 is data showing the results of X-ray diffraction measurement of the silicon substrate.

On the other hand, a buffer film PRT made of tantalum, silicon, and oxygen and an amorphous alloy film LY made of tantalum silicon (Ta _1-x Si _x ; x = 0.3) on the glass substrate SUB according to the present invention. In the model structure in which (TaSi) is laminated (FIG. 3 (b)), as shown in FIG. 7, immediately after film formation, tantalum silicon has an amorphous structure, so the surface is difficult to crack and is extremely difficult in the atmosphere. Since it is in a stable state and hardly oxidized by oxygen in the atmosphere, it has a depth from the film surface that is a boundary between the amorphous alloy film LY (TaSi) and the buffer film PRT. The compositional molar ratio of tantalum and silicon (generally tantalum 0.7, silicon 0.3) was shown over the entire area up to a thickness of 200 nm.

  Next, as in the case of using the tantalum thin film described above, after the heat treatment that continuously applies a temperature of 400 ° C. in the atmosphere for 30 minutes to the model structure, as shown in FIG. Furthermore, although the composition ratio (content) of oxygen is high in the very surface layer of the amorphous alloy film LY (TaSi), the composition ratio of tantalum and silicon is substantially uniform over almost the entire region up to a depth of 200 nm (generally Tantalum 0.7, silicon 0.3). That is, it was found that oxidation progressed only in the surface layer of the amorphous alloy film LY (TaSi).

  For example, when the crystallinity of a tantalum silicon film formed with a film thickness of several hundreds of nanometers on a silicon substrate using a sputtering method is measured using an X-ray diffractometer, as shown in FIG. Also in the result of line diffraction, a relatively gentle peak showing a wide and relatively low intensity (about 5000 CPS) is obtained in the vicinity of approximately 35 to 40 deg, which is in the vicinity of the diffraction angle (2θ) peculiar to tantalum silicon. Therefore, the tantalum silicon thin film formed on the substrate has a relatively low crystallinity, that is, tantalum and silicon are in solid solution so as to be amorphous. The generation is suppressed, and oxygen does not enter the film even by the heat treatment in the atmosphere as described above, and a uniform composition of tantalum and silicon is maintained over almost the entire area of the film. It is considered to have been.

  Therefore, by applying the amorphous alloy film made of tantalum silicon according to the present invention, the oxidation does not proceed excessively at the time of anodic bonding and the film quality does not become brittle. Since both tantalum and silicon alone can be bonded to oxygen during anodic bonding, oxygen molecules contained in the glass substrate to be bonded and the amorphous alloy film can be bonded well to obtain a good bonding state. At the same time, it is possible to realize a chemical reaction apparatus with good bonding strength by preventing deterioration of the quality of the amorphous alloy film.

  In the experimental data shown in FIG. 6, a minute peak (intensity of about 4000 CPS) is recognized around 65 deg, which is not a diffraction angle peculiar to tantalum, and also in the experimental data shown in FIG. A minute peak (intensity of about 4000 CPS) is observed. When X-ray diffraction measurement is performed on this peak using a single silicon substrate applied to form a thin film of each of the above metal materials, as shown in FIG. 10, a sharp peak peculiar to silicon is around a diffraction angle of 55 deg. Observed. As a result, the minute peak in FIG. 9 is presumed to be due to silicon atoms constituting the substrate, and the minute peak in FIG. 6 is not known in detail, but the impurities in the X-ray diffractometer or silicon substrate. It is presumed to be caused by impurities contained therein.

Next, the tension accompanying the crystallinity in the tantalum film and the tantalum silicon film described above is verified.
FIG. 11 shows experimental results showing stress characteristics of tantalum silicon applied to the amorphous alloy film according to the present embodiment and tantalum as a comparison target.

  In the configuration in which the amorphous alloy film is formed on one surface side of the glass substrate as in the above-described model structure (FIG. 3), the inventors of the present application have the film quality of the amorphous alloy film and the stress applied to the substrate. As a result, for example, when the thickness of the glass substrate is approximately 0.7 mm or more, a metal film made of tantalum (Ta) having a thickness of about several hundred nm (100 nm to 1 μm) is sputtered. In the case where the thickness of the glass substrate is approximately 0.2 mm or less in order to reduce the size and thickness of the chemical reaction device, the flatness of the glass substrate is maintained satisfactorily. It was confirmed that, under the same process conditions, the flatness of the glass substrate was impaired and warping occurred.

Such a phenomenon is caused by the tension (extension force or compression force) accompanying the relatively high crystallinity of the tantalum film as shown in the X-ray diffraction data (see FIG. 6). In FIG. 11, as indicated by SPa, an extremely high stress (a difference in tensile or compressive stress; a stress value of approximately 28 × 10 ¹⁰ dyn / cm ² ) is generated between the glass substrate and the tantalum film. Conceivable.

On the other hand, for tantalum silicon applied to the amorphous alloy film according to the present invention, the film thickness is approximately several hundred nm (100 nm to 1 μm) on a glass substrate having a plate thickness of approximately 0.2 mm or less. When the stress generated when an amorphous alloy film made of tantalum silicon is formed by sputtering is measured, as shown in the X-ray diffraction data (see FIG. 9), the tantalum silicon thin film has a comparative crystallinity. Therefore, as shown in SPb in FIG. 11, almost no stress is generated between the substrate and the glass substrate (substantially 0 dyn /). cm ² stress value). Therefore, the flatness of the glass substrate can be maintained well.

  In this way, by forming an amorphous (low crystallinity) oxide metal thin film over the entire area of the film on a relatively thin substrate, crystal grain boundaries generated inside the film are suppressed, and oxygen in the atmosphere is reduced. It is possible to prevent deterioration of the film quality by suppressing the progress of oxidation due to, and to reduce the tension caused by the crystallinity, reduce the stress generated between the substrate and maintain the flatness of the substrate well can do.

In particular, the inventors of the present application have made various studies in view of the above experimental results, and as a result, sputtered an amorphous alloy film on a glass substrate having a relatively thin plate thickness of 0.2 mm or less. When formed by the method, the thin film material applied to the amorphous alloy film is a metal compound having an amorphous material, more specifically, for example, a metal compound of tantalum and silicon (Ta _1-x Si _x ), When the composition ratio is set to silicon 0.3 with respect to tantalum 0.7 (x = 0.3), the bonding state with the substrate as the amorphous alloy film, the oxidation resistance in the atmosphere, the substrate It was concluded that the material is optimal in terms of the stress that occurs between the two and the ease of the manufacturing process.

From the above, the chemical reaction apparatus according to the present embodiment includes a main substrate made of a glass substrate on which a groove-like reaction channel is formed and a glass substrate for closing the open end of the reaction channel. It is made of an amorphous single layer metal film, for example, tantalum silicon Ta _1-x Si _x (more preferably, having a composition ratio of silicon 0.3 to tantalum 0.7) between the sub-substrate. By having a configuration in which an amorphous alloy film is interposed, the amorphous alloy film can be formed on the sub-substrate by a single sputtering process, and in the atmosphere until anodic bonding with the main substrate. Even when transported and stored (in an atmosphere containing oxygen), it is difficult to oxidize not only on the surface of the amorphous alloy film but also on the inside of the film, thus making it easier to handle the substrate and simplifying the process. Or low It is possible to reduce the list of.

In addition, since the amount of metal that is distributed on the surface of the amorphous alloy film and directly contributes to anodic bonding is set by the composition ratio of tantalum silicon, the amorphous state of tantalum and oxygen molecules in the glass substrate Can be controlled to realize a good bonding state.
In addition, since the tantalum silicon film formed on the substrate by a sputtering method has an amorphous film quality with low crystallinity, the stress value is extremely low, and the influence of tension on the sub-substrate can be suppressed. And the occurrence of warping of the sub-board can be suppressed.
Furthermore, according to the chemical reaction device according to the present embodiment, since a glass substrate can be applied as the main substrate and the sub-substrate, compared with the case where an expensive silicon substrate or the like is applied as the main substrate, the chemical reaction The device can be manufactured at low cost.

<Application example to power system>
Next, a specific example when the chemical reaction device according to the present invention is applied to a power supply system including a fuel cell will be described.
FIG. 12 is a schematic block diagram showing the overall configuration of an embodiment of a power supply system (fuel cell system) to which the chemical reaction apparatus according to the present invention can be applied. Here, a configuration provided with a polymer electrolyte fuel cell employing a fuel reforming supply system as a power supply system will be described.

As shown in FIG. 12, the power supply system (fuel cell system) 100 according to this embodiment is roughly a fuel cartridge in which hydrocarbon-based power generation fuel such as methanol CH ₃ OH and water H ₂ O are individually enclosed. (Power generation fuel container) 120, a reforming section (reforming means) 112 for reforming the power generation fuel (methanol CH ₃ OH) taken out from the fuel cartridge 120 to extract hydrogen gas H ₂ , and hydrogen gas A power generation cell unit (fuel cell main body) 111 composed of a solid polymer fuel cell that generates electrical energy by an electrochemical reaction using H ₂ and oxygen O ₂ , and an electrochemical reaction in the power generation cell unit 111 and with water recovery H _{2 O} by-product, water recovery for controlling the supply state of the water to the electrolyte membrane at least the power generation cell section 111 (an ion exchange membrane) Control unit (water recovery control unit) 113, fuel supply control unit (fuel supply control unit) 114 that controls the supply state of the fuel for power generation enclosed in fuel cartridge 120 to the reforming unit, and at least fuel cartridge 120 The water supply control part (water supply control means) 115 which controls the supply state to the electrolyte membrane of the power generation cell part 111 of the enclosed water is provided.

  Here, the power generation cell unit 111, the reforming unit 112, the water recovery control unit 113, the fuel supply control unit 114, and the water supply control unit 115 constitute a power generation module 110, and a fuel cartridge 120 is provided to the power generation module 110. Is configured to be detachable. Therefore, as will be described later, the power generation module 110 is built in, for example, an electronic device in which the fuel cell system according to the present invention is mounted, and has the same usability as when a dry battery or a battery is replaced. The fuel and water for power generation are replenished by attaching / detaching (changing) only the fuel cartridge 120 to / from the power generation module).

Hereinafter, each configuration will be described in detail.
(Power generation cell unit 111)
FIG. 13 is a schematic configuration diagram showing a solid polymer fuel cell applicable to the power supply system according to the present embodiment.
As shown in FIG. 13, a power generation cell unit (fuel cell main body) 111 applied to the power supply system (fuel cell system) according to this embodiment is roughly a carbon electrode to which catalyst fine particles such as platinum, platinum / ruthenium are attached. An anode electrode ELa comprising a cathode electrode ELc comprising a carbon electrode to which catalyst fine particles such as platinum are attached, and a film-like electrolyte membrane (ion exchange membrane) LYi interposed between the anode electrode ELa and the cathode electrode ELc The hydrogen gas H ₂ obtained by reforming the power generation fuel (methanol CH ₃ OH) by the fuel supply control unit 114 and the reforming unit 112 described later is supplied to the anode electrode ELa side, On the other hand, the cathode electrode ELc side is configured such that, for example, oxygen O ₂ in the atmosphere (air) is directly and constantly supplied to the outside air.

Here, in the power generation cell unit 111 according to the present embodiment, methanol CH ₃ OH taken out from the fuel cartridge 120 (the fuel sealing unit 121) is reformed by the reforming unit 112, and only hydrogen gas H ₂ is anode. is supplied to the electrode ELa, fuel cartridge 120 (water containment section 122) water H _{2 O} is directly retrieved from, or water H ₂ produced as a byproduct along with the electric power generation operation in the power generation cell section 111 O is recovered and supplied to the electrolyte membrane LYi. The supply state (supply timing and supply amount) of hydrogen gas H ₂ and water H ₂ O to the power generation cell unit 111 is determined by a fuel supply control unit 114, a water supply control unit 115, or a water recovery control unit 113, which will be described later. It is controlled appropriately.

The electrochemical reaction related to the power generation operation in the fuel cell of the fuel reforming supply system having such a configuration is represented by the following chemical reaction formula (1) when hydrogen gas H ₂ is supplied to the anode ELa. As described above, the electrons (e ⁻ ) are separated by the catalytic reaction to generate hydrogen ions H ^+, which pass through the electrolyte membrane LYi to the cathode electrode ELc side, and the electrons e ⁻ by the carbon electrode constituting the anode electrode ELa. Is taken out and supplied to the load LD.
2H ₂ → 4H ⁺ + 4e ⁻ (1)

On the other hand, when air (oxygen O ₂ ) is supplied to the cathode electrode ELc, as shown in the following chemical reaction formula (2), the electrons e ⁻ that have passed through the load LD and the hydrogen that has passed through the electrolyte membrane LYi by the catalyst. The ions H ⁺ and oxygen O ₂ in the air react to produce water (H ₂ O) as a by-product.
4H ⁺ + O ₂ + 4e ⁻ → 2H ₂ O (2)

Here, the series of electrochemical reactions described above (formulas (1) and (2)) proceed under relatively low temperature conditions of approximately 60 to 80 ° C., and by-products other than electrical energy (electric power) are Basically water H ₂ O only. Note that the electrical energy extracted by such an electrochemical reaction depends on the amount of hydrogen gas H ₂ supplied to the anode electrode ELa of the power generation cell unit 111.

In the power generation operation described above, it is necessary that H ₃ O ⁺ ions be generated by the water H ₂ O (moisture) intervening in the conduction (passage) of hydrogen ions H ⁺ in the electrolyte membrane LYi. In order to promote the electrochemical reaction and increase the power generation efficiency, it is known that the atmosphere in the vicinity of the electrolyte membrane LYi needs to be in a steam saturated state (wet state).

Therefore, in the present embodiment, as a method for supplying water to the power generation cell unit 111 (electrolyte membrane LYi), the water supply control unit 115 causes the fuel cartridge 120 to be supplied when the system is started (at the start of power generation and immediately after the start). Water H ₂ O sealed in the water sealing part 122 is directly supplied, and the electrolyte membrane LYi is controlled to be maintained in a predetermined wet state (water vapor saturation state), and the power generation operation in the power generation cell unit 111 is in a steady state. After the transition to, the water recovery control unit 113 is supplied with the power generation operation in the power generation cell unit 111 and the recovered water H ₂ O is supplied, so that the electrolyte membrane LYi is in a predetermined wet state (water vapor saturation state). ).

(Reformer 112)
FIG. 14 is a conceptual diagram illustrating a configuration example of a reforming unit applied to the power supply system according to the present embodiment. FIG. 15 illustrates a chemical reaction in the reforming unit applied to the power supply system according to the present embodiment. It is a conceptual diagram which shows an example. FIG. 16 is a schematic diagram showing a configuration example when the chemical reaction device according to the present invention is applied to the reforming unit of the power supply system according to the present embodiment.

As shown in FIG. 14, the reforming unit 112 applied to the power supply system according to the present embodiment heats and vaporizes methanol CH ₃ OH and a small amount of water H ₂ O supplied from the fuel cartridge 120. vessels and (evaporator) 112a, a predetermined catalytic reaction from the vaporized methanol (methanol gas) and water (water vapor), and the fuel reformer 112b for generating hydrogen gas _{H 2,} in the fuel reformer 112b, hydrogen CO remover that generates hydrogen gas H ₂ and carbon dioxide CO ₂ by a predetermined catalytic reaction from carbon monoxide CO generated as a by-product during generation of gas H ₂ , water H ₂ O, and oxygen O ₂ 112c, and a thin film heater H for controlling temperature conditions for promoting a chemical reaction in at least the fuel vaporizer 112a, the fuel reformer 112b, and the CO remover 112c It is configured to include Hb, and Hc, and a combustor 112d, a.

Here, the thin film heaters Ha and Hb generate heat by power from a power source (not shown) (for example, an auxiliary power source such as a storage battery) in the initial stage of reforming, and the reformed hydrogen is supplied to generate the power generation cell. After the unit 111 generates power, the heat generation temperature is controlled by switching the electric energy (electric power) generated in the power generation cell unit 111 as a power source to generate heat. Further, the fuel unit 112d has a fuel vaporization function (for example, a function of vaporizing methanol under a temperature condition of about 90 ° C.) for vaporizing methanol CH ₃ OH supplied from the fuel cartridge 120, and the vaporized methanol gas and the atmosphere Unreacted hydrogen remaining by oxidation reaction (combustion reaction) with oxygen O ₂ contained therein or on the anode electrode ELa side of the power generation cell unit 111 without contributing to the chemical reaction shown in the above formula (1) The exothermic temperature is controlled by an oxidation reaction (combustion reaction) between the gas H ₂ and oxygen O ₂ contained in the atmosphere. The heat generation in the combustor 112d may be due to combustion of only one of the above-described methanol gas or hydrogen gas, or may be a combination of both, or the fuel vaporizer 112a and The reaction temperature of the fuel reformer 112b and the CO remover 112c may be individually controlled in an individual reaction chamber to individually control the heat generation temperature.

  In addition to such a temperature control mechanism, after the power generation cell unit 111 generates power by supplying reformed hydrogen, the remaining hydrogen that has not been used for power generation in the power generation cell unit 111 and the outside are taken in from the outside. By supplying oxygen in the air to the combustor 112d, a combustion reaction of hydrogen is caused in the combustor 112d to generate a high calorific value. Therefore, after power generation, the combustor 112d becomes the main heat source of the reforming unit 112, and the thin film heater is supplementarily heated by Ha and Hb to perform fine adjustment (fine adjustment) of the temperature condition. In addition, desired temperature conditions (temperature conditions of about several hundred degrees C. described later) can be realized with relatively little electric energy (electric power), and consumption of generated electric energy can be suppressed.

In the reforming section 112 having such a configuration, the catalytic reaction in the fuel reformer 112b is realized by an endothermic steam reforming reaction, and the catalytic reaction in the CO remover 112c is an exothermic water shift reaction and an exothermic reaction. Realized by selective oxidation reaction.
Specifically, in the case of generating hydrogen gas H ₂ from, for example, methanol CH ₃ OH and water H ₂ O in the reforming unit 112, first, as shown in FIG. In the evaporation process in the vaporizer 112a, the above-described thin film heater Ha and the combustor 112d are controlled so that the heating temperature of the fuel vaporizer 112a (for example, the temperature of the boiling point of methanol CH ₃ OH and water H ₂ O) (for example, By setting the temperature to about 120 ° C., the methanol CH ₃ OH and water H ₂ O supplied from the fuel cartridge 120 are individually heated, or the mixed liquid is heated at once to be vaporized.

Next, in the steam reforming reaction process in the fuel reformer 112b, the thin film heater Hb and the combustor 112d are controlled to be set to a temperature condition of about 280 ° C., so that the following chemical reaction formula (3) is shown. Thus, hydrogen H ₂ and a small amount of carbon dioxide CO ₂ are generated. In this steam reforming reaction, a small amount of carbon monoxide CO is generated as a by-product in addition to hydrogen H ₂ and carbon dioxide CO ₂ .
CH ₃ OH + H ₂ O → 3H ₂ + CO ₂ (3)

Therefore, in order to remove such harmful by-products, as shown in FIG. 15 (b), in the CO remover 112c, the thin film heater Hc and the combustor 112d are controlled, and the temperature condition is about 180 ° C. As shown in the following chemical reaction formula (4), water H ₂ O (water vapor) is reacted with carbon monoxide to generate carbon dioxide CO ₂ and hydrogen H _2. reaction process, and, with respect to carbon monoxide CO which has not been converted into carbon dioxide and hydrogen in the aqueous shift reaction, by reacting the oxygen O ₂ in the air, the selective oxidation reaction process to produce carbon dioxide CO ₂ is Executed.
CO + H ₂ O → CO ₂ + H ₂ (4)
CO + (1/2) O ₂ → CO ₂ (5)

(Fuel supply control unit 114)
As shown in FIG. 12, the fuel supply control unit 114 has a function as an interface for detachably connecting the fuel cartridge 120 (the fuel sealing unit 121) and the power generation module 110, and at least in the fuel cartridge 120. It has a function of controlling the timing and amount of supply of the enclosed fuel for power generation (methanol CH ₃ OH) to the reformer 112 described above.

(Water supply control unit 115)
As shown in FIG. 12, the water supply control unit 115 has a function as an interface for detachably connecting the fuel cartridge 120 (water sealing unit 122) and the power generation module 10, and at least in the fuel cartridge 210. It has a function of controlling the timing and supply amount of the sealed water H ₂ O supplied to the reforming unit 112 and the power generation cell unit 111 described above.

  Specifically, the fuel supply control unit 114 and the water supply control unit 115 are, for example, a fuel supply path and a water supply between the fuel cartridge 120 and the reforming unit 112 and between the fuel cartridge 120 and the power generation cell unit 111. A configuration including a liquid pump, a flow rate control valve, or the like (or a supply mechanism having a function equivalent to these) can be applied to the path.

(Water recovery control unit 113)
As shown in FIG. 12, the water recovery control unit 113 recovers water H ₂ O generated as a by-product in the electrochemical reaction related to the power generation operation in the power generation cell unit 111, and at least returns it to the power generation cell unit 111. Supplying again, the electrolyte membrane (ion exchange membrane) is kept in a predetermined wet state. Furthermore, some of the water recovered by the water recovery control unit 113 may be supplied to the reforming unit 112 (fuel vaporizer 112a, CO remover 112c) and used for each chemical reaction. Specifically, the water recovery control unit 113 can be configured to include a liquid pump, a flow rate control valve, a flow path switching valve, or the like (or a supply mechanism having the same function as these).

(Fuel cartridge 120)
As shown in FIG. 12, the fuel cartridge 120 includes a fuel sealing portion 121 made of a package in which methanol CH ₃ OH, which is a power generation fuel, is sealed, and a water sealing made of a package in which a predetermined amount of water H ₂ O is sealed. For example, these are integrated and configured to be detachable from the power generation module.

  In the fuel cell system according to the present embodiment, it is desirable that the fuel for power generation runs out and the fuel cartridge 120 removed from the power generation module 110 is recovered through a predetermined recycling route and properly disposed. Even if it is discarded without being collected, it is formed from a material that does not affect the environment, such as the generation of harmful substances (for example, chlorinated organic compounds, heavy metals, etc.) or has little effect on the environment. It is desirable that

  In addition, as a power generation fuel used in the fuel cell system according to the present embodiment, at least in the power generation cell unit composed of the fuel cell described above, electrical energy can be generated with high energy conversion efficiency, and power generation After the fuel cartridge containing the fuel was used, it was dumped or landfilled in nature, and the remaining power generation fuel leaked into the atmosphere, soil, or water, or was incinerated and discharged into the atmosphere. Even if it is a case, it is desirable that the fuel does not become a pollutant to the natural environment. Specifically, in addition to the above methanol, hydrocarbon liquid fuels such as ethanol and butanol (alcohols) are good. Can be applied to.

  In the power supply system having such a configuration, each of the fuel vaporizer 112a, the fuel reformer 112b, the CO remover 112c, and the combustor 112d of the reforming unit 112 has the above-described chemical reaction device according to the present invention. It is possible to satisfactorily apply a structure in which the (reaction part) is applied and these are laminated together.

  That is, as shown in FIG. 16, for example, the fuel vaporizer 112a described above includes a main substrate (glass substrate) SBa having a reaction channel formed on one surface side, and a thin film heater Ha made of a heating resistor on one surface side. The formed sub-substrate (glass substrate) CLa and a bonding film MLa provided on the other surface side of the main substrate SBa and in which amorphous tantalum silicon is bonded to oxygen atoms on the other surface side of the sub-substrate CLa by anodic bonding. The configuration of a chemical reaction device (microreactor) including the above can be applied.

  Also for the fuel reformer 112b described above, a main substrate (glass substrate) SBb having a reaction channel formed on one surface side and a sub-substrate having a bonding film MLb similar to the bonding film MLa formed on one surface side ( A configuration of a chemical reaction apparatus (microreactor) in which glass substrate (CLb) is bonded by anodic bonding can be applied. The thin film heater Hb made of a thin film resistor is, for example, a sub-combustor of the combustor 112d formed in close contact with the fuel reformer 112b in order to adjust and control the thermal energy transmitted to the fuel reformer 112b. It is formed on the other surface side of the substrate (glass substrate) CLd.

  In addition, with respect to the CO remover 112c described above, a main substrate (glass substrate) SBc having a reaction channel formed on one surface side, and a bonding film MLc similar to the bonding film MLa is formed on one surface side, and the other surface A configuration of a chemical reaction device (microreactor) in which a sub-substrate (glass substrate) CLc on which a thin-film heater Hc made of a thin-film resistor is formed is bonded by anodic bonding can be applied.

  Further, in the above-described combustor 112d, a main substrate (glass substrate) SBd having a reaction channel formed on one surface side, a bonding film MLd similar to the bonding film MLa is formed on one surface side, and on the other surface side. A configuration of a chemical reaction device (microreactor) in which a sub-substrate (glass substrate) CLc on which a thin film heater Hb for the fuel reformer 112b is formed is bonded by anodic bonding can be applied. As for the fuel vaporization function provided in the combustor 112d (denoted by “112e” in the drawing for the sake of convenience), as with the fuel vaporizer 112a described above, a main substrate having a reaction channel formed on one surface side (Glass substrate) SBe and a sub-substrate (glass substrate) CLe on which one side of a bonding film MLe similar to the bonding film MLa is formed and a thin film heater He made of a heating resistor is formed on the other side A configuration of a chemical reaction apparatus (microreactor) bonded by anodic bonding can be applied.

  And each structure of these reforming parts 112 considers the transmission state of the thermal energy emitted from thin film heaters Ha, Hb, Hc and combustor 112d, combustor 112d, fuel reformer 112b, CO removal 112c, a fuel vaporizer 112a, and a fuel vaporization function 112e are stacked in this order. Here, the technique of anodic bonding can be favorably applied to the bonding between the components. In FIG. 16, illustration of the configuration of the fluid substance introduction section and the discharge section in each chemical reaction apparatus is omitted, but for example, it corresponds to the series of chemical reactions shown in FIGS. 14 and 15 described above. In addition, it is possible to satisfactorily apply a configuration including a flow path communicating between the layers.

  Thus, the substrates of the chemical reaction devices constituting the reforming unit 112 in the power supply system 100 and the chemical reaction devices can be satisfactorily bonded to each other. A highly reliable power supply system that can generate hydrogen gas from a hydrocarbon-based power generation fuel such as methanol and supply it well to the power generation cell section through a desired chemical reaction Can do.

  Further, according to such a configuration, the thickness of the substrate of each component of the reforming unit 112 can be reduced and the size and thickness can be significantly reduced, and an inexpensive substrate material can be used with a simple manufacturing process. Therefore, for example, the mounting of the power supply system in a portable electronic device such as a notebook personal computer or a portable information terminal can be facilitated and promoted.

  In the power supply system according to the present embodiment, a fuel reforming supply system that generates power using a predetermined fluid substance (hydrogen gas or the like) generated by a reforming unit to which the chemical reaction apparatus according to the present invention is applied. However, the present invention is not limited to this, and the present invention is not limited to this, and is based on thermal energy (temperature difference associated with the combustion reaction of a fluid substance generated using a chemical reaction device (microreactor)). Power generation), or by mechanical energy conversion that generates electric power by rotating the generator using pressure energy associated with combustion reaction, etc. (internal combustion engines such as gas combustion turbines, rotary engines, Stirling engines, external combustion engines) Power generation), which converts fluid energy and thermal energy of power generation fuel FL into electric power using the principle of electromagnetic induction, etc. Can be applied thermoacoustic effect power generation, etc.) or the like, a power supply system having a variety of forms.

It is the schematic which shows one Embodiment of the chemical reaction apparatus which concerns on this invention, and its manufacturing process. It is the schematic which shows an example of the plane pattern (flow path shape) of the reaction flow path applied to the chemical reaction apparatus which concerns on this embodiment. It is the schematic which shows the model structure used in order to verify the characteristic of the metal material (metallic material) applicable to the amorphous alloy film which concerns on this embodiment. It is a figure which shows the composition ratio immediately after film-forming at the time of applying a tantalum to an amorphous alloy film. It is a figure which shows the composition ratio after the predetermined heat processing at the time of applying a tantalum to an amorphous alloy film. It is data which shows the result of the X-ray-diffraction measurement for verification of the crystallinity of the tantalum film | membrane formed on the board | substrate. It is a figure which shows the composition ratio immediately after film-forming when tantalum silicon is applied to an amorphous alloy film. It is a figure which shows the composition ratio after the predetermined heat processing at the time of applying a tantalum silicon to an amorphous alloy film. It is data which shows the result of the X-ray-diffraction measurement for verification of the crystallinity of the tantalum silicon film formed on the board | substrate. It is data which shows the result of the X-ray-diffraction measurement of a silicon substrate. It is an experimental result which shows the stress characteristic in the tantalum silicon applied to the amorphous alloy film which concerns on this embodiment, and the tantalum used as the comparison object. 1 is a schematic block diagram showing an overall configuration of an embodiment of a power supply system (fuel cell system) to which a chemical reaction device according to the present invention can be applied. It is a schematic block diagram which shows the polymer electrolyte fuel cell applicable to the power supply system which concerns on this embodiment. It is a conceptual diagram which shows the example of 1 structure of the modification | reformation part applied to the power supply system which concerns on this embodiment. It is a conceptual diagram which shows an example of the chemical reaction in the modification | reformation part applied to the power supply system which concerns on this embodiment. It is the schematic which shows one structural example at the time of applying the chemical reaction apparatus which concerns on this invention to the modification | reformation part of the power supply system which concerns on this embodiment. It is a schematic block diagram which shows the basic structure of the microreactor in a prior art. It is a conceptual diagram which shows the anodic bonding method applied to the manufacturing process of the microreactor in a prior art.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Main board | substrate 11 Reaction flow path 12 Catalyst layer 20 Subboard | substrate 21 Bonding film 30, Ha, Hb, Hc Thin film heater 100 Power supply system 111 Power generation cell part 112 Reformer part 112a Fuel vaporizer 112b Fuel reformer 112c CO remover 112d Combustor

Claims (11)

In a chemical reaction device that generates a chemical reaction in a predetermined reaction channel,
at least,
A first substrate having a groove-like reaction channel formed on one side thereof;
A second substrate provided opposite to the first substrate and closing an open end of the reaction channel;
An amorphous bonding film interposed between the first substrate and the second substrate and bonded to an oxygen atom contained in one of the first substrate and the second substrate;
A chemical reaction apparatus comprising: The bonding film is formed into a thin film by sputtering on the substrate on one side of the first substrate and the second substrate, and is bonded to the substrate on the other side by anodic bonding. The chemical reaction apparatus according to claim 1, wherein: The chemical reaction apparatus according to claim 1, wherein the bonding film is a solution of tantalum and silicon. 4. The chemical reaction apparatus according to claim 3, wherein the bonding film is set to a composition ratio of silicon 0.3 with respect to tantalum 0.7. The chemical reaction device has a configuration in which a predetermined catalyst substance is attached and formed on the inner wall surface of the reaction flow path,
5. The chemical reaction device according to claim 1, wherein the chemical reaction converts a first fluid substance into a second fluid substance by a catalytic reaction with the catalyst substance. 6. A chemical reaction device for generating a chemical reaction for converting a first fluid substance into a second fluid substance in a predetermined reaction channel is provided, and electric energy is generated using the second fluid substance generated by the chemical reaction device. A power system that generates
The chemical reaction apparatus includes at least
A first substrate made of a glass substrate having a groove-like reaction channel formed on one side thereof;
A second substrate comprising a glass substrate provided opposite to the first substrate and closing an open end of the reaction channel;
An amorphous bonding film interposed between the first substrate and the second substrate and bonded to an oxygen atom contained in one of the first substrate and the second substrate;
A power supply system comprising a reaction unit consisting of: The bonding film is a bonding metal film formed by sputtering on one of the first substrate and the second substrate, and the other of the first substrate and the second substrate by anodic bonding. The power supply system according to claim 6, wherein the first substrate and the second substrate are bonded to each other in combination with oxygen atoms. 8. The power supply system according to claim 6, wherein the bonding film is made of a compound of tantalum and silicon. 9. The power supply system according to claim 8, wherein the bonding film is set to a composition ratio of silicon 0.3 with respect to tantalum 0.7. The chemical reaction apparatus has a configuration in which a predetermined catalytic substance is attached and formed on the inner wall surface of the reaction flow path, and a temperature adjustment layer is formed in a region corresponding to the reaction flow path. The power supply system according to any one of claims 6 to 9. The power supply system according to any one of claims 6 to 10, wherein the chemical reaction device has a configuration in which a plurality of the reaction units are stacked and each of the reaction units generates a different chemical reaction. .

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