WO2014073095A1 - Thermoelectric conversion module and method for manufacturing same - Google Patents

Thermoelectric conversion module and method for manufacturing same Download PDF

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Publication number
WO2014073095A1
WO2014073095A1 PCT/JP2012/079173 JP2012079173W WO2014073095A1 WO 2014073095 A1 WO2014073095 A1 WO 2014073095A1 JP 2012079173 W JP2012079173 W JP 2012079173W WO 2014073095 A1 WO2014073095 A1 WO 2014073095A1
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Prior art keywords
thermoelectric conversion
vanadium oxide
type
conversion element
glass layer
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PCT/JP2012/079173
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French (fr)
Japanese (ja)
Inventor
正 藤枝
内藤　孝
拓也 青柳
沢井　裕一
護 吉本
晃史 松田
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株式会社日立製作所
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Priority to PCT/JP2012/079173 priority Critical patent/WO2014073095A1/en
Priority to JP2014545525A priority patent/JPWO2014073095A1/en
Publication of WO2014073095A1 publication Critical patent/WO2014073095A1/en

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
    • H10N10/80—Constructional details
    • H10N10/85—Thermoelectric active materials
    • H10N10/851—Thermoelectric active materials comprising inorganic compositions
    • H10N10/855—Thermoelectric active materials comprising inorganic compositions comprising compounds containing boron, carbon, oxygen or nitrogen
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
    • H10N10/01—Manufacture or treatment

Definitions

  • the present invention relates to a thermoelectric conversion module and a method of manufacturing the same.
  • thermoelectric conversion material generates electricity when the temperature difference is given (Seebeck effect) and cools when electricity flows (Peltier effect). Therefore, it is used as a thermoelectric conversion element such as a power generation element or a cooling element. There is. According to the Seebeck effect, since heat can be directly converted to electricity, power generation and the like using exhaust heat can be performed, and a thermoelectric conversion element is expected as one of clean energy technologies.
  • a thermoelectric conversion material forming the thermoelectric conversion element for example, a bismuth-tellurium material, a bismuth-antimony material, a bismuth-tellurium-antimony material, etc. are known.
  • thermoelectric conversion module provided with a thermoelectric conversion element
  • a bulk type thermoelectric conversion element is often used.
  • microfabrication is difficult, and therefore, there are cases where miniaturization of the thermoelectric conversion elements is difficult.
  • the power output density is low and the unit price of power generation is high.
  • Patent Document 1 describes a thermoelectric conversion element having thermoelectric conversion material particles having a diameter of 1 ⁇ m to 10 ⁇ m and a coating layer having an average film thickness of 1 ⁇ m or less, which coats the periphery of the thermoelectric conversion material particles. .
  • thermoelectric conversion element In the thermoelectric conversion element described in Patent Document 1, metal oxide fine particles are used as a binder. However, such metal oxide particles do not have the thermoelectric conversion ability, and the thermoelectric conversion efficiency may be lowered. Further, Patent Document 1 does not describe reducing the size of the thermoelectric conversion element to improve the output density of electric power.
  • the present invention has been made in view of the above-mentioned problems, and an object of the present invention is to provide a thermoelectric conversion module capable of improving the output density of electric power as compared with the prior art and a method of manufacturing the same.
  • thermoelectric conversion element material containing vanadium oxide crystallized glass is used, and the electrode and the thermoelectric conversion element are joined by at least amorphous vanadium oxide contained in the vanadium oxide crystallized glass. I found that I could solve the problem.
  • thermoelectric conversion module which can improve the output density of electric power conventionally can be provided, and its manufacturing method.
  • thermoelectric conversion module It is a perspective view of a thermoelectric conversion module concerning this embodiment. It is a graph obtained in the temperature rising process of the differential thermal analysis with respect to the vanadium oxide crystallized glass used for the thermoelectric conversion element which concerns on this embodiment. They are a cross-sectional photograph by (a) electron microscope, and the (b) schematic diagram of the junction interface vicinity of the electrode and vanadium oxide crystallized glass in the thermoelectric conversion element which concerns on this embodiment. It is a figure which shows the manufacturing method of the thermoelectric conversion module which concerns on 1st Embodiment. It is a figure which shows the manufacturing method of the thermoelectric conversion module which concerns on 2nd Embodiment. It is a figure which shows the manufacturing method of the thermoelectric conversion module which concerns on 3rd Embodiment. It is a figure explaining the thermoelectric-characteristics evaluation method about the thermoelectric conversion module produced in Example 1.
  • thermoelectric conversion element according to the present embodiment will be described, and then a method of manufacturing the same will be described.
  • some members may be omitted or simplified for convenience of description and for convenience of illustration, or may be changed or modified without departing from the scope of the invention.
  • FIG. 1 is a perspective view of a thermoelectric conversion module according to the present embodiment.
  • the thermoelectric conversion module 100 includes a plurality of thermoelectric conversion element materials 10 configured by including vanadium oxide crystallized glass containing vanadium oxide crystals and an amorphous material, and the thermoelectric conversion element material 10.
  • a support substrate 11 to be supported and fixed (arranged), and an electrode 12 connected to the thermoelectric conversion element material 10 and connected to an external load 20 consuming the electromotive force generated in the thermoelectric conversion element material 10 Become.
  • the thermoelectric conversion element is configured to include the thermoelectric conversion element materials 10 a and 10 b and the electrode 12.
  • thermoelectric conversion element material 10 in this embodiment contains the vanadium oxide crystallized glass as mentioned above, the vanadium oxide crystallized glass contains a vanadium oxide crystal and an amorphous material. It contains amorphous vanadium oxide.
  • the thermoelectric conversion element material 10 and the electrode 12 are joined via at least the amorphous material contained in the thermoelectric conversion element material 10.
  • thermoelectric conversion element material 10 in the present embodiment is configured to include N-type vanadium oxide crystallized glass or P-type vanadium oxide crystallized glass. These vanadium oxide crystallized glasses can be obtained by heat treating amorphous vanadium oxide glasses under predetermined conditions.
  • thermoelectric conversion module 100 is comprised by the thermoelectric conversion element containing the thermoelectric conversion element material 10.
  • thermoelectric conversion element materials 10 a and the thermoelectric conversion element materials 10 b are alternately arranged in a matrix on the support substrate 11. Then, in the y direction, the anode of the thermoelectric conversion element material 10a and the cathode of the thermoelectric conversion element material 10b are electrically connected via the electrode 12b, and the cathode of the thermoelectric conversion element material 10a and the anode of the thermoelectric conversion element material 10b And are electrically connected via the electrode 12b. Further, at the end in the y direction, the anode of the thermoelectric conversion element material 10a and the cathode of the thermoelectric conversion element material 10b adjacent in the x direction are electrically connected via the electrode 12b.
  • thermoelectric conversion element material 10 included in the thermoelectric conversion module 100 is an N-type thermoelectric conversion element material (hereinafter referred to as “N-type material”) 10 a configured to include N-type vanadium oxide crystallized glass; And P-type thermoelectric conversion element material (hereinafter, referred to as "P-type material”) 10b configured to include P-type vanadium oxide crystallized glass.
  • N-type material N-type thermoelectric conversion element material
  • P-type material P-type thermoelectric conversion element material
  • the N-type material 10 a is an N-type semiconductor containing free electrons. In the N-type material 10a, free electrons generated on the high temperature side move toward the low temperature. As a result, current can flow through the N-type material 10a.
  • the P-type material 10 b is a P-type semiconductor containing holes. In the P-type material 10 b, the contained holes move to a lower temperature. Thus, current can flow through the P-type material 10b.
  • power generation is performed by connecting the N-type material 10a and the P-type material 10b by the electrode 12 (described later). The electromotive force obtained by the power generation is used in the external load 20 (resistor, storage battery, etc.).
  • the N-type material 10 a and the P-type material 10 b are alternately connected in series by the electrodes 12 fixed to the substrate 11.
  • the N-type material 10a is fixed to the end of the current extraction negative electrode 12c (electrode 12) fixed to the support substrate 11a.
  • the N-type material 10a is fixed to the adjacent P-type material 10b by the electrode 12b fixed to the support substrate 11b.
  • the P-type material 10b is fixed to an adjacent N-type material 10a other than the N-type material 10a by an electrode 12a fixed to a support substrate 11a.
  • the N-type material 10a and the P-type material 10b are connected in series in the same manner, and it is more preferable than connecting the positive electrode 12d and the negative electrode 12c for current extraction in parallel. High electromotive force can be taken out.
  • thermoelectric conversion element material 10 the vanadium oxide crystallized glass contained in the thermoelectric conversion element material 10 will be described with reference to FIG.
  • FIG. 2 is a graph obtained in the temperature rising process of differential thermal analysis (DTA) for the vanadium oxide crystallized glass contained in the thermoelectric conversion element material 10.
  • the DTA measurement was performed using a vanadium oxide crystallized glass (target sample) and ⁇ -alumina (reference sample) contained in the thermoelectric conversion element material 10 at a temperature rising rate of 5 K / min in the air atmosphere.
  • the amounts of the target sample and the reference sample used for the measurement were each 650 mg.
  • T c the starting temperature of the first exothermic peak crystallization temperature T c.
  • each temperature be temperature calculated
  • the characteristic temperatures (glass transition point T g , yield point T d , softening point T s and crystallization temperature T c ) described in the present specification are based on the above-mentioned definitions.
  • the thermoelectric conversion element material 10 contains crystallized vanadium oxide glass which normally has a softening point and is crystallized. This is because the vanadium oxide glass is fired by heating it at a temperature higher than the softening point and lower than the crystallization temperature, and then heat treated at a temperature higher than the crystallization temperature to precipitate vanadium oxide crystals. It is possible to use a vanadium oxide crystallized glass (that is, a thermoelectric conversion element material) in which the crystal and the mixture are mixed.
  • the vanadium oxide crystallized glass is contained in the thermoelectric conversion element material 10 in the present embodiment.
  • the thermoelectric conversion element material 10 contains a vanadium oxide crystal and an amorphous vanadium oxide as an amorphous material.
  • the amorphous material contained in the thermoelectric conversion element material 10 is not limited to amorphous vanadium oxide, and may be another material.
  • the amorphous material is preferably an amorphous vanadium oxide.
  • thermoelectric conversion element material 10 may contain any material as long as the effects of the present invention are not significantly impaired.
  • the N-type element 10a V 2 O 5 , M x V 2 O 5 , M 3 Fe 4 (PO 4 ) 6 , M 2 (PO 4 ) O, V 2 (PO 4 ) O And at least one crystal selected from the group consisting of M 2 CuO 4 and MAl 2 O 4 .
  • M is a metal element of any of aluminum, iron, arsenic, antimony, bismuth, tungsten, molybdenum, manganese, nickel, copper, silver, an alkali metal and an alkaline earth metal.
  • the P-type element 10b may include at least one crystal selected from the group consisting of VO 2 and V 2 O 3 .
  • thermoelectric conversion element material 10 may contain glass other than vanadium oxide glass.
  • the amorphous material (this point will be described later with reference to FIG. 3) present at the bonding interface between the thermoelectric conversion element material 10 and the electrode 12 Not limited to amorphous vanadium oxide, it may be an amorphous material composed of another glass material.
  • vanadium oxide glass having no softening point can be used in combination.
  • thermoelectric conversion element material 10 containing vanadium oxide crystallized glass can be produced by applying, for example, a paste containing powdered amorphous vanadium oxide glass onto the electrode 12 and heat treating it. By this heat treatment, the amorphous vanadium oxide glass is crystallized to obtain a vanadium oxide crystallized glass containing vanadium oxide crystals.
  • amorphous vanadium oxide usually remains at the grain boundaries of the obtained vanadium oxide crystal.
  • other arbitrary components can be used together to powder-form vanadium oxide glass to apply
  • the application method at the time of application may be any method.
  • a thick film dry film resist used in the production of a rib of a plasma display panel can be used.
  • a dry photoresist patterned at a position where the thermoelectric conversion element material 10 is to be formed can be placed on the support substrate 11, and the paste can be poured into the patterning and applied.
  • the dry film resist is insulating and has a low thermal conductivity, so that there is an advantage that the removal of the dry film resist which may remain after the preparation of the thermoelectric conversion material is unnecessary.
  • the film to be used may be a thin film laminated and laminated.
  • a high heat resistant resin film such as polyimide can be used.
  • the support substrate 11 supports and fixes the thermoelectric conversion element material 10 and the electrode 12. Specifically, the thermoelectric conversion element material 10 (10a, 10b) is formed to be sandwiched by the support substrate 11 (11a, 11b) to which the electrode 12 (12a, 12b) is fixed.
  • the support substrate 11 is configured of a low temperature side support substrate 11a in contact with a heat sink (not shown) and the like, and a high temperature side support substrate 11b in contact with a heater (not shown) and the like.
  • the support substrate 11 is made of an insulating substrate.
  • a conductive substrate may be used, and in this case, an insulating layer is provided between the conductive substrate and the electrode 11.
  • the support substrate 11 is preferably made of a material excellent in heat conductivity.
  • a substrate for example, a ceramic substrate made of alumina, aluminum nitride or the like, a silicon substrate having an oxide layer, a metal substrate and the like can be mentioned.
  • a substrate for example, a resin substrate or the like
  • excellent in flexibility can also be used.
  • the electrode 12 is configured in a pattern shape in the present embodiment, and connects the thermoelectric conversion element material 10 (the anode and the adjacent cathode) so as to bridge the electromotive force generated in the thermoelectric conversion element material 10 It supplies the external load 20.
  • the electrode 12 a material which hardly reacts with the vanadium oxide glass is used. Specifically, examples thereof include titanium, tungsten, tantalum, chromium, silicon, aluminum, and nitrides, silicides thereof, and alloys thereof.
  • the electrodes 12 may be arranged and fixed to the support substrate 11 in any manner.
  • a metal film can be formed on the support substrate 11 by vapor deposition, sputtering or the like.
  • the formed metal film is patterned into a desired shape by photolithography, etching or the like to form an electrode 12 with a desired shape.
  • the electrode 12 may be formed by printing an electrode pattern on the support substrate 11 using, for example, screen printing, inkjet printing, a dispenser, or the like using a metal paste and baking it.
  • a metal paste used when printing on the support substrate 11 for example, a general-purpose metal paste, a paste composed of a conductive filler and a vanadium oxide glass, and the like can be used. Examples of the metal used include silver, copper and aluminum.
  • thermoelectric conversion element material 10 and the electrode 12 are bonded to a part of the bonding interface by containing an amorphous material (amorphous vanadium oxide in this embodiment). This will be specifically described with reference to FIG.
  • FIG. 3 is (a) a sectional photograph by an electron microscope and (b) a schematic view in the vicinity of the bonding interface between the electrode and the vanadium oxide crystallized glass in the thermoelectric conversion element according to the present embodiment.
  • crystallization 101 (vanadium oxide crystal) contained in the thermoelectric conversion element material 10 is partially abbreviate
  • FIG. 3 shows that vanadium oxide glass is coated on an electrode made of titanium and fired, and then heat treatment is performed in vacuum to form N-type vanadium oxide crystallized glass. is there.
  • thermoelectric conversion element material 10 is configured to include a large number of vanadium oxide crystals 101. However, at the bonding interface between the thermoelectric conversion element material 10 and the electrode 12, an amorphous 102 of vanadium oxide is present. More specifically, in the present embodiment, the thermoelectric conversion element material 10 is joined to the electrode 12 at least through the amorphous 102 of the vanadium oxide contained.
  • thermoelectric conversion element material 10 is [2. Although it mentions later in the manufacturing method of a thermoelectric conversion element, it can form by, for example, forming the layer containing an amorphous vanadium oxide glass on the electrode 12, and heat-processing after that. Therefore, in the thermoelectric conversion module 100 of the present embodiment, the amorphous 102 can be made to exist at the bonding interface by controlling the heating condition at the time of the heat treatment.
  • thermoelectric conversion element material 10 of the present embodiment it is difficult to use the conventional method, for example, by using a low cost process such as screen printing, coating, etc.
  • a low cost process such as screen printing, coating, etc.
  • short element length (height is about 0.1 mm, for example) And so on can be produced.
  • the output density is generally proportional to the amount of heat flowing through the thermoelectric conversion element material as well as the thermoelectric conversion efficiency. Therefore, high output density can be achieved by increasing the heat flux passing through the thermoelectric conversion element material 10 of the present embodiment and forming the small thermoelectric conversion element material 10 at a high density per unit area. .
  • the cost in a manufacturing process is cheap, the power generation unit price can be reduced significantly.
  • thermoelectric conversion element a method of manufacturing a thermoelectric conversion element according to the present embodiment (hereinafter simply referred to as “the manufacturing method of the present embodiment”) will be described with reference to the drawings.
  • the amorphous material contained in the thermoelectric conversion element of this embodiment is preferably amorphous vanadium oxide. Therefore, in the following description, the manufacturing method of the present embodiment will be described by using amorphous vanadium oxide as an example of the amorphous material.
  • the manufacturing method of the present embodiment is formed in the glass layer forming step of forming a vanadium oxide glass layer containing vanadium oxide glass on the electrode 12 disposed and fixed on the support substrate 11 and the glass layer forming step.
  • a vanadium oxide glass layer is heat-treated to form a vanadium oxide crystallized glass layer containing vanadium oxide crystals and an amorphous material (in this embodiment, amorphous vanadium oxide), and And a heat treatment step of causing the amorphous material to exist in at least a part of the bonding interface.
  • a powder of vanadium oxide glass is made into a paste.
  • the powder contains amorphous vanadium oxide glass.
  • the paste is applied on the electrode by, for example, a stencil printing method, a screen printing method, or a patterning method using a thick film resist used in rib production of a plasma display panel. Thereby, a vanadium oxide glass layer containing vanadium oxide glass is formed.
  • the paste to be applied usually comprises vanadium oxide glass and a solvent.
  • a resin binder may be appropriately contained.
  • the particle size of the vanadium oxide glass to be contained is not particularly limited, but in consideration of the coating property at the time of coating, the average particle size is preferably 5 ⁇ m or less.
  • the solvent contained is not particularly limited, but butyl carbitol acetate and ⁇ -terpineol are preferable.
  • the resin binder to be contained is not particularly limited, but ethyl cellulose and nitrocellulose are preferable. However, when ⁇ -terpineol is used as the solvent, the resin binder may not be used.
  • ⁇ Heat treatment process> heat treatment is performed on the formed vanadium oxide glass layer.
  • the conditions of the heat treatment are not particularly limited as long as vanadium oxide crystals can be precipitated in the layer.
  • the substrate coated with the paste is dried at a temperature of about 423 K for 10 minutes to evaporate the solvent.
  • temporary baking is performed at a temperature of about 573 K for 30 minutes to remove the binder, and main baking is performed at a temperature equal to or higher than the softening point Ts of the glass, whereby a vanadium oxide glass layer is formed.
  • main baking is performed at a temperature equal to or higher than the softening point Ts of the glass, whereby a vanadium oxide glass layer is formed.
  • main baking is performed at a temperature equal to or higher than the softening point Ts of the glass, whereby a vanadium oxide glass layer is formed.
  • main baking is performed at a temperature equal to or higher than the softening point Ts of the glass, whereby a vanadium oxide glass layer is
  • the atmosphere during the heat treatment is not particularly limited, but in the case of forming an N-type crystallized vanadium oxide glass, for example, in the air, in vacuum or in an inert gas (nitrogen, argon, etc.) atmosphere is preferable.
  • a reducing atmosphere such as a hydrogen gas atmosphere is preferably used.
  • a glass powder of P and N which has been prepared in advance and another glass powder which softens at a temperature at which the glass powder melts are mixed,
  • the mixed glass powder may be made into a paste by the above method, and it may be applied and fired.
  • thermoelectric conversion module 100 In order to improve the durability of the thermoelectric conversion module 100, it is preferable to seal the ends of the pair of supporting substrates 11a and 11b with glass. Specifically, a glass paste for sealing (or a glass frit for sealing may be applied) is applied to the end portions of the support substrates 11a and 11b, and then it is fired and sealed in an electric furnace. At this time, it is preferable to seal the inside of the thermoelectric conversion module 100 while evacuating from the viewpoint of improving durability and heat insulation. Moreover, you may bake and seal, applying a load.
  • the glass for sealing is a glass excellent in water resistance.
  • thermoelectric conversion element material 10 can be reduced as compared to the case where N-type vanadium oxide crystallized glass is directly generated by heat treatment in vacuum or in an inert gas atmosphere.
  • N-type vanadium oxide crystallized glass can be newly formed continuously.
  • a paste containing vanadium oxide glass is applied onto a part of the electrodes 12 formed on the support substrate 11 and fired in a reducing atmosphere to obtain P-type vanadium oxide crystallized glass
  • the paste is again applied on the electrode at a position separated (for example, adjacent) to the P-type vanadium oxide crystallized glass, and then the whole is fired.
  • heat treatment is performed at a crystallization temperature of the glass in vacuum or in an inert gas atmosphere to form an N-type vanadium oxide crystallized glass.
  • thermoelectric conversion element materials 10 are connected in series so that the polarities of the elements 10 alternate. Thereafter, by firing at a softening point T s a temperature above the glass, it is possible to form the thermoelectric conversion module 100.
  • the supporting substrate 11a in which a plurality of N-type vanadium oxide crystallized glasses are formed on the electrode 12a, and the supporting substrate 11b in which the P-type vanadium oxide crystallized glass is formed on the electrode 12b are separated. Then, the support substrates 11a and 11b are bonded to each other so that the polarities of the thermoelectric conversion element material 10 are alternately connected in series. Thereafter, the same and fired at the softening point T s temperature above the glass, it is possible to form the thermoelectric conversion module 100.
  • thermoelectric conversion element material 10a and the thermoelectric conversion element material 10b may be manufactured by using the same material but by changing the heat treatment conditions.
  • thermoelectric conversion element material 10a and the thermoelectric conversion element material 10b can also be manufactured by using different materials and making the heat treatment conditions the same.
  • thermoelectric conversion element material 10 determination of the polarity (N-type and P-type) of the thermoelectric conversion element material 10 is performed by measuring the Seebeck coefficient of the thermoelectric conversion element material 10 using a Seebeck coefficient measuring machine. I went. If the Seebeck coefficient is positive it is P-type, and if the Seebeck coefficient is negative it is N-type.
  • thermoelectric conversion module containing individually manufactured N-type and P-type thermoelectric conversion element materials
  • Table 1 shows the raw material composition of the glass used, and the characteristic points (glass transition point, deformation point, softening point and crystallization temperature) of the glasses (TE1, TE2, EL1, and EL2) obtained from differential thermal analysis curves.
  • EL1 is sealing glass for sealing the edge part of a thermoelectric conversion module
  • EL2 is glass for electrode formation for forming the electrode provided on a support substrate.
  • the glasses TE1, TE2, EL1 and EL2 were prepared as follows.
  • the composition of the glass melt is uniform in an electric furnace in which 200 g of the mixed material powder having the composition of Table 1 is put in a platinum crucible and heated to 1373 K for TE1 glass and TE2 glass, and 1073 K for EL1 glass and EL2 glass.
  • the mixture was melted for 1 hour while being stirred. Then, it was cooled and solidified on a stainless steel plate heated to 423K to 475K. Furthermore, the melted glass was pulverized to about several ⁇ m by a stamp mill and a jet mill. In addition, it was confirmed by X-ray diffraction that all the glasses were also amorphous.
  • a mixed solution of 50% by mass of ethylcellulose (EC) and butyl carbitol acetate (BCA) (mass ratio of EC to BCA is 4%) is blended with TE2 glass powder having a softening point, and thermoelectric conversion is performed.
  • Glass paste A for device material was prepared.
  • a conductive paste B for electrode formation was prepared.
  • EL2 glass powder shown in Table 1 and silver particles with a particle diameter of several ⁇ m having a volume ratio of 80% with respect to the EL2 glass powder are mixed, and 50 mass% of ethyl cellulose ( A mixed solution of EC and butyl carbitol acetate (BCA) (weight ratio of EC to BCA is 4%) was formulated.
  • a glass paste for sealing upper and lower support substrates an appropriate amount of EL-glass powder having a softening point lower than the softening point of the N-type and P-type crystallized glass powder or the glass powder of the conductive paste.
  • An ⁇ -terpineol solvent was added to prepare a sealing glass paste C.
  • thermoelectric conversion module 100 was produced by the method shown in FIG. An aluminum plate was used as a supporting substrate, and two aluminum substrates 11a and 11b having an alumina layer formed on one surface by anodizing treatment were used. First, conductive paste B was applied by screen printing on an alumina layer (not shown in FIG. 4) formed on the surface of an aluminum substrate. Then, it was dried in the air at a temperature of about 423 K for 10 minutes to volatilize the solvent, and temporarily baked at a temperature of about 573 K for 30 minutes to remove the binder. Thereafter, at a temperature of 740K is the glass softening point T s or more make this baked for 30 minutes, the electrode 12a shown in FIG. 4 (a), to form 12b.
  • the patterned heat-dissipation dry film resist 301 was attached to the surfaces of the support substrates 11a and 11b.
  • the thickness of the film was slightly thicker than the desired thickness of the thermoelectric conversion module in consideration of the volatilization amount of the solvent and the like of the glass paste A.
  • the glass paste A portion indicated by reference numeral 303
  • the sealing glass paste C portion indicated by reference numeral 304
  • the poured portion of the sealing glass paste C is a pattern of the end.
  • the support substrate 11a and the support substrate 11b were separately worked.
  • the support substrate 11a was subjected to heat treatment in the air at a temperature of 823 K for 2 hours in an electric furnace.
  • a thermoelectric conversion element material including N-type vanadium oxide crystallized glass of 0.5 mm ⁇ 0.5 mm ⁇ 0.1 mm (height) on the support substrate 11a (corresponding to the first support substrate) 10a was obtained.
  • a sealing layer 305 was also obtained.
  • the dry film resist disappears during heat treatment, so that there is no deformation of the paste end (corner) that occurs when extruding the paste from the mask, which may occur in screen printing, and a thermoelectric conversion module with excellent film thickness uniformity is formed. We were able to.
  • thermoelectric conversion element material 10a was subjected to X-ray diffraction, and Fe 3 Fe 4 (PO 4 ) in addition to V 2 O 5 and Cu x V 2 O (0.26 ⁇ x ⁇ 0.55) 6 , it was found that crystals such as Cu 3 Fe 4 (PO 4 ) 6 , Al 2 CuO 4 , FeAl 2 O 4 (0 ⁇ x ⁇ 1) were precipitated.
  • thermoelectric conversion element material containing 0.5 mm ⁇ 0.5 mm ⁇ 0.1 mm (height) of P-type vanadium oxide crystallized glass on the support substrate 11 b (corresponding to the second support substrate) 10b was obtained.
  • the dry film resist 301 stuck on the support substrate 11b remained, it was made to melt
  • thermoelectric conversion element material 10b When X-ray diffraction was performed on the obtained thermoelectric conversion element material 10b, crystals of Fe 2 PO 5 , Fe 2 (PO 4 ) O, V 2 (PO 4 ) O, etc. were precipitated besides V 2 O 3 It turned out that I was doing.
  • thermoelectric conversion module 100 shown in FIG. 4F was obtained.
  • thermoelectric conversion element material 10 The bonding interface between the thermoelectric conversion element material 10 and the electrode 12 of the thermoelectric conversion module 100 was observed using an electron microscope. As a result, many vanadium oxide crystals were observed, but it was found that the amorphous vanadium oxide and the electrode 12 were joined at a part of the joining interface. As a result, it has been found that miniaturization can be achieved as described above, and high output density can be achieved. Furthermore, it turned out that the unit price of power generation can be significantly reduced. Moreover, since the thermoelectric conversion element material 10a and the thermoelectric conversion element material 10b were separately manufactured, the non-staying could be made better.
  • Example 2 Production of a thermoelectric conversion module including N-type and P-type thermoelectric conversion element materials produced simultaneously]
  • the N-type thermoelectric conversion element material 10 a and the P-type thermoelectric conversion element material 10 b were separately manufactured, but in Example 2, the N-type thermoelectric conversion element material 10 a and the P-type thermoelectric conversion The conversion element material 10b was continuously produced. That is, first, the thermoelectric conversion element material 10b containing P-type vanadium oxide crystallized glass is formed, and the whole is newly fired while maintaining its polarity, and the thermoelectric conversion containing N-type vanadium oxide crystallized glass The element material 10a was formed. The same glass paste A, conductive paste B and sealing glass paste C as used in Example 1 were used.
  • thermoelectric conversion module 200 was produced by the method shown in FIG.
  • a dry film resist 301 patterned was attached onto a support substrate 11a shown in FIG. 5B.
  • every other glass paste A (portion indicated by reference numeral 303) for the thermoelectric conversion element was poured into the pattern 302 in the dry film resist 301.
  • the sealing paste C is poured into the end, nothing is poured at this time.
  • the binder was removed.
  • thermoelectric conversion element material 10 b containing 0.5 mm ⁇ 0.5 mm ⁇ 0.1 mm (height) of P-type vanadium oxide crystallized glass was obtained. .
  • a glass paste A for a thermoelectric conversion element (a portion indicated by reference numeral 303 in FIG. 5 (e)) and a sealing glass paste C (FIG. 5 (e))
  • a portion indicated by reference numeral 304 was poured. Then, in the same manner as in Example 1, the binder was removed.
  • Material 10a was obtained.
  • a sealing layer 305 was also obtained. At this time, even if the support substrate 11a is provided in the vacuum electric path, the polarity of the P-type thermoelectric conversion element material 10b which has already been formed is maintained without changing the polarity of the P-type thermoelectric conversion element material 10b. The remaining dry film resist was dissolved in a solvent and removed.
  • thermoelectric conversion module 200 shown in FIG. 5H was obtained.
  • Example 2 As in Example 1 described above, also in Example 2, the bonding interface between the thermoelectric conversion element material 10 of the thermoelectric conversion module 200 and the electrode 12 was observed using an electron microscope. As a result, a large amount of vanadium oxide crystals were observed, but it was found that the amorphous vanadium oxide and the electrode 12 were joined at a part of the joining interface as in Example 1. As a result, it has been found that miniaturization can be achieved as described above, and high output density can be achieved. Furthermore, it turned out that the unit price of power generation can be significantly reduced. In addition, since both of the thermoelectric conversion element materials 10a and 10b are manufactured on a single support substrate 11a, positioning at the time of bonding the support substrate 11b can be facilitated.
  • Example 3 Preparation of a thermoelectric conversion module including N-type and P-type thermoelectric conversion element materials simultaneously manufactured.
  • the N-type thermoelectric conversion element material 10 a and the P-type thermoelectric conversion element material 10 b are both formed using the glass paste A. Therefore, in Example 3, the material for the N-type thermoelectric conversion element material 10a and the material for the P-type thermoelectric conversion element material 10b are different, and a thermoelectric conversion module is manufactured in the same manner as in Example 1 above. Three hundred were prepared.
  • the powder of TE1 glass was subjected to heat treatment at a temperature of 823 K for 2 hours in an electric furnace of hydrogen gas flow.
  • a powder of P-type vanadium oxide crystallized glass was obtained.
  • this powder is referred to as "P-type glass powder”.
  • crystals such as Fe 2 PO 5 , Fe 2 (PO 4 ) O, and V 2 (PO 4 ) O were precipitated. I found that.
  • thermoelectric conversion element material 10 A predetermined amount of TE2 glass in Table 1 was mixed with each of the N-type glass powder and the P-type glass powder to obtain a material of the thermoelectric conversion element material 10. Specifically, 10% to 20% by volume of TE2 glass powder is mixed with N-type glass powder, and further, 50% by mass of ethyl cellulose (EC) and butyl carbitol are mixed with these mixed powders.
  • the glass paste D is a material of the N-type thermoelectric conversion element material 10 a.
  • P-type glass powder was similarly compounded to prepare a glass paste E.
  • the glass paste E is a material of the P-type thermoelectric conversion element material 10 b.
  • thermoelectric conversion module 300 was produced by the method shown in FIG.
  • the dry film resist 301 patterned was attached onto the support substrate 11a. Then, in the pattern 302 of the dry resist film 301, as shown in FIG. 6C, the glass paste D (portion indicated by reference numeral 306 in FIG. 6C) and the glass paste E (FIG. 6 (FIG. c) In the middle, a portion indicated by reference numeral 307 is alternately poured. Furthermore, at the end, the sealing glass paste C prepared in Example 1 (the portion indicated by reference numeral 304 in FIG. 6C) was poured.
  • the main baking can also be performed in vacuum or in an inert gas atmosphere.
  • the dry film resist does not disappear but remains, but may remain as described above.
  • thermoelectric conversion module 300 shown in FIG. 6F was obtained.
  • Example 3 As in Example 1 described above, also in Example 3, the bonding interface between the thermoelectric conversion element material 10 of the thermoelectric conversion module 300 and the electrode 12 was observed using an electron microscope. As a result, a large amount of vanadium oxide crystals were observed, but it was found that the amorphous vanadium oxide and the electrode 12 were joined at a part of the joining interface as in Example 1. As a result, it has been found that miniaturization can be achieved as described above, and high output density can be achieved. Furthermore, it turned out that the unit price of power generation can be significantly reduced. In addition, since both of the thermoelectric conversion element materials 10a and 10b are manufactured on the single support substrate 11a, positioning at the time of bonding the support substrate 11b can be facilitated. In addition, since the thermoelectric conversion element materials 10a and 10b can be manufactured by one heat treatment, the process can be simplified.
  • thermoelectric conversion modules 100, 200, and 300 manufactured in the first to third embodiments each include the N-type thermoelectric conversion element material 10a and the P-type thermoelectric conversion element material 10b. Therefore, as a representative of them, the thermoelectric characteristic evaluation was performed on the thermoelectric conversion module 100 manufactured in the first embodiment.
  • thermoelectric conversion module 100 in which 1000 N-type thermoelectric conversion element materials 10a and 1000 P-type thermoelectric conversion element materials 10b were connected in series was produced. And the produced thermoelectric conversion module 100 was installed as shown in FIG.
  • FIG. 7 is a diagram for explaining a method of evaluating the thermoelectric characteristics of the thermoelectric conversion module manufactured in the first embodiment.
  • FIG. 7 is partially changed and described from the shape of the thermoelectric conversion module 100 shown in FIG.
  • thermoelectric conversion module 100 was placed on the copper block 702, and the heater 701 was placed on the thermoelectric conversion module 100.
  • the copper block 702 is mounted on the heat sink 703. Therefore, the heat from the heater 701 is supplied to the thermoelectric conversion element material 10 from the supporting substrate 11 b side of the thermoelectric conversion module 100. That is, the supporting substrate 11b side is at the high temperature side. On the other hand, the supporting substrate 11a side is at the low temperature side.
  • thermoelectric characteristics were performed as follows.
  • the temperature of the heater 701 was set to 423 K (150 ° C.), and the temperature difference ⁇ T between the support substrates 11 a and 11 b in the thermoelectric conversion module 100 was set to 50 K.
  • the heat flux Q flowing from the thermoelectric conversion module 100 in the direction of the heat sink 703 and the output voltage (electromotive force) P measured by the voltmeter 704 were measured.
  • the heat flux Q was 10 W / cm 2 and the output voltage P was 8V.
  • conversion efficiency ⁇ was calculated based on these values.
  • the thermoelectric conversion module 100 includes the thermoelectric conversion element 12 including amorphous vanadium oxide glass (amorphous material) at the bonding interface between the thermoelectric conversion element material 10 and the electrode 12. Therefore, as described above, downsizing can be achieved, and high output density can be achieved. Furthermore, the unit price of power generation can be significantly reduced.
  • a total of 2000 thermoelectric conversion element materials 10 of P-type and N-type were manufactured, but by further downsizing, for example, about 20,000 total thermoelectric conversion modules are to be manufactured. You can also. As a result, the output density can be further improved, and the conversion efficiency can be further improved.
  • thermoelectric conversion element material thermoelectric conversion element 11a, 11b Supporting substrate 12, 12a, 12b, 12c electrode (thermoelectric conversion element) 100 thermoelectric conversion module 200 thermoelectric conversion module 300 thermoelectric conversion module

Abstract

The present invention provides a thermoelectric conversion module capable of realizing higher power output density than the prior art and a method for manufacturing same. A thermoelectric conversion module characterized in being provided with a supporting substrate, a plurality of thermoelectric conversion element materials and an electrode. The thermoelectric conversion element materials are disposed on the supporting substrate and comprise vanadium oxide crystallized glass containing vanadium oxide crystal and an amorphous material. The electrode, which is disposed on the supporting substrate, interconnects the thermoelectric conversion element materials, and is connected to an external load consuming an electromotive force generated in the thermoelectric conversion element materials. The thermoelectric conversion element materials and the electrode are joined together via at least the amorphous material contained in the thermoelectric conversion element material.

Description

熱電変換モジュール及びその製造方法Thermoelectric conversion module and method of manufacturing the same
　本発明は、熱電変換モジュール及びその製造方法に関する。 The present invention relates to a thermoelectric conversion module and a method of manufacturing the same.
　熱電変換材料は、温度差を与えると発電し（ゼーベック効果）、逆に、電気を流すと冷える（ペルチェ効果）という性質を示すことから、発電素子、冷却素子等の熱電変換素子として利用されている。ゼーベック効果によれば、熱を電気に直接変換することができるため、排熱を利用した発電等が可能であり、熱電変換素子は、クリーンエネルギー技術の１つとして期待されている。熱電変換素子を構成する熱電変換材料としては、例えば、ビスマス－テルル系材料、ビスマス－アンチモン系材料、ビスマス－テルル－アンチモン系材料等が知られている。 The thermoelectric conversion material generates electricity when the temperature difference is given (Seebeck effect) and cools when electricity flows (Peltier effect). Therefore, it is used as a thermoelectric conversion element such as a power generation element or a cooling element. There is. According to the Seebeck effect, since heat can be directly converted to electricity, power generation and the like using exhaust heat can be performed, and a thermoelectric conversion element is expected as one of clean energy technologies. As a thermoelectric conversion material forming the thermoelectric conversion element, for example, a bismuth-tellurium material, a bismuth-antimony material, a bismuth-tellurium-antimony material, etc. are known.
　ゼーベック効果による起電力は、熱電変換素子の高温部と低温部との温度差に比例する。そのため、熱電変換素子を備える熱電変換モジュールにおいては、バルク形の熱電変換素子が用いられることが多い。しかしながら、バルク形の熱電変換素子においては、微細加工が困難であるため、熱電変換素子の小型化が困難なことがある。その結果、電力の出力密度が小さく、発電単価が高くなる。 The electromotive force due to the Seebeck effect is proportional to the temperature difference between the high temperature part and the low temperature part of the thermoelectric conversion element. Therefore, in a thermoelectric conversion module provided with a thermoelectric conversion element, a bulk type thermoelectric conversion element is often used. However, in the case of bulk thermoelectric conversion elements, microfabrication is difficult, and therefore, there are cases where miniaturization of the thermoelectric conversion elements is difficult. As a result, the power output density is low and the unit price of power generation is high.
　そこで、電力の出力密度をあげるため、高効率な熱電変換素子に関する技術が知られている。例えば特許文献１には、直径が１μｍ以上１０μｍ以下の熱電変換材料粒子と、前記熱電変換材料粒子の周囲を被膜する、平均膜厚１μｍ以下の被膜層とを有する熱電変換素子が記載されている。 Then, in order to raise the output density of electric power, the technique regarding a highly efficient thermoelectric conversion element is known. For example, Patent Document 1 describes a thermoelectric conversion element having thermoelectric conversion material particles having a diameter of 1 μm to 10 μm and a coating layer having an average film thickness of 1 μm or less, which coats the periphery of the thermoelectric conversion material particles. .
特開２０１０－２２５７１９号公報Unexamined-Japanese-Patent No. 2010-225719
　特許文献１に記載の熱電変換素子においては、結着剤として金属酸化物微粒子を用いている。しかし、このような金属酸化物微粒子は熱電変換能を有さないため、熱電変換効率が低下することがある。また、特許文献１には、熱電変換素子を小型化させて電力の出力密度を向上させることは記載されていない。 In the thermoelectric conversion element described in Patent Document 1, metal oxide fine particles are used as a binder. However, such metal oxide particles do not have the thermoelectric conversion ability, and the thermoelectric conversion efficiency may be lowered. Further, Patent Document 1 does not describe reducing the size of the thermoelectric conversion element to improve the output density of electric power.
　本発明は前記課題に鑑みて為されたものであり、本発明の課題は、電力の出力密度を従来よりも向上可能な熱電変換モジュール及びその製造方法を提供することにある。 The present invention has been made in view of the above-mentioned problems, and an object of the present invention is to provide a thermoelectric conversion module capable of improving the output density of electric power as compared with the prior art and a method of manufacturing the same.
　本発明者らは前記課題を解決するべく鋭意検討を行った。その結果、バナジウム酸化物結晶化ガラスを含む熱電変換素子材料とし、電極と熱電変換素子とを、前記バナジウム酸化物結晶化ガラスに含まれる、少なくとも非晶質のバナジウム酸化物によって接合することで前記課題を解決できることを見出した。 The present inventors diligently studied to solve the above problems. As a result, the thermoelectric conversion element material containing vanadium oxide crystallized glass is used, and the electrode and the thermoelectric conversion element are joined by at least amorphous vanadium oxide contained in the vanadium oxide crystallized glass. I found that I could solve the problem.
　本発明によれば、電力の出力密度を従来よりも向上可能な熱電変換モジュール及びその製造方法を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the thermoelectric conversion module which can improve the output density of electric power conventionally can be provided, and its manufacturing method.
本実施形態に係る熱電変換モジュールの斜視図である。It is a perspective view of a thermoelectric conversion module concerning this embodiment. 本実施形態に係る熱電変換素子に用いられるバナジウム酸化物結晶化ガラスに対する示差熱分析の昇温過程で得られるグラフである。It is a graph obtained in the temperature rising process of the differential thermal analysis with respect to the vanadium oxide crystallized glass used for the thermoelectric conversion element which concerns on this embodiment. 本実施形態に係る熱電変換素子における、電極とバナジウム酸化物結晶化ガラスとの接合界面近傍の（ａ）電子顕微鏡による断面写真及び（ｂ）模式図である。They are a cross-sectional photograph by (a) electron microscope, and the (b) schematic diagram of the junction interface vicinity of the electrode and vanadium oxide crystallized glass in the thermoelectric conversion element which concerns on this embodiment. 第１実施形態に係る熱電変換モジュールの製造方法を示す図である。It is a figure which shows the manufacturing method of the thermoelectric conversion module which concerns on 1st Embodiment. 第２実施形態に係る熱電変換モジュールの製造方法を示す図である。It is a figure which shows the manufacturing method of the thermoelectric conversion module which concerns on 2nd Embodiment. 第３実施形態に係る熱電変換モジュールの製造方法を示す図である。It is a figure which shows the manufacturing method of the thermoelectric conversion module which concerns on 3rd Embodiment. 実施例１において作製した熱電変換モジュールについての熱電特性評価方法を説明する図である。It is a figure explaining the thermoelectric-characteristics evaluation method about the thermoelectric conversion module produced in Example 1. FIG.
　以下、本発明を実施するための形態（本実施形態）を説明するが、本実施形態は以下の内容に何ら制限されるものでない。 Hereinafter, although the form (this embodiment) for implementing this invention is demonstrated, this embodiment is not restrict | limited at all to the following content.
　はじめに、本実施形態に係る熱電変換素子について説明し、次いで、その製造方法について説明する。また、適宜参照する図は、説明の簡略化及び図示の便宜上、一部の部材を省略又は簡略化して記載したり、発明の要旨を逸脱しない範囲で変更して記載したりすることがある。 First, the thermoelectric conversion element according to the present embodiment will be described, and then a method of manufacturing the same will be described. In the drawings referred to as appropriate, some members may be omitted or simplified for convenience of description and for convenience of illustration, or may be changed or modified without departing from the scope of the invention.
［１．熱電変換素子］
　図１は、本実施形態に係る熱電変換モジュールの斜視図である。本実施形態に係る熱電変換モジュール１００は、バナジウム酸化物結晶と非晶質材料とを含むバナジウム酸化物結晶化ガラスを含んで構成される複数の熱電変換素子材料１０と、熱電変換素子材料１０が支持固定（配置）される支持基板１１と、熱電変換素子材料１０同士を接続するとともに、熱電変換素子材料１０において発生した起電力が消費される外部負荷２０に接続される電極１２とを備えてなる。なお、熱電変換素子は、熱電変換素子材料１０ａ，１０ｂと電極１２とを備えて構成される。 [1. Thermoelectric conversion element]
FIG. 1 is a perspective view of a thermoelectric conversion module according to the present embodiment. The thermoelectric conversion module 100 according to the present embodiment includes a plurality of thermoelectric conversion element materials 10 configured by including vanadium oxide crystallized glass containing vanadium oxide crystals and an amorphous material, and the thermoelectric conversion element material 10. A support substrate 11 to be supported and fixed (arranged), and an electrode 12 connected to the thermoelectric conversion element material 10 and connected to an external load 20 consuming the electromotive force generated in the thermoelectric conversion element material 10 Become. The thermoelectric conversion element is configured to include the thermoelectric conversion element materials 10 a and 10 b and the electrode 12.
　また、本実施形態における熱電変換素子材料１０は、前記のようにバナジウム酸化物結晶化ガラスを含んでいるが、バナジウム酸化物結晶化ガラスには、バナジウム酸化物結晶と、非晶質材料としての非晶質のバナジウム酸化物とが含まれている。そして、熱電変換素子材料１０と電極１２とは、熱電変換素子材料１０に含まれる少なくとも前記非晶質材料を介して接合している。 Moreover, although the thermoelectric conversion element material 10 in this embodiment contains the vanadium oxide crystallized glass as mentioned above, the vanadium oxide crystallized glass contains a vanadium oxide crystal and an amorphous material. It contains amorphous vanadium oxide. The thermoelectric conversion element material 10 and the electrode 12 are joined via at least the amorphous material contained in the thermoelectric conversion element material 10.
　なお、詳細は後記するが、本実施形態における熱電変換素子材料１０は、Ｎ型のバナジウム酸化物結晶化ガラス、又は、Ｐ型のバナジウム酸化物結晶化ガラスを含んで構成されるものである。これらのバナジウム酸化物結晶化ガラスは、非晶質のバナジウム酸化物ガラスを所定条件下で熱処理することにより、得ることができる。そして、熱電変換素子材料１０を含む熱電変換素子により、熱電変換モジュール１００が構成される。 Although details will be described later, the thermoelectric conversion element material 10 in the present embodiment is configured to include N-type vanadium oxide crystallized glass or P-type vanadium oxide crystallized glass. These vanadium oxide crystallized glasses can be obtained by heat treating amorphous vanadium oxide glasses under predetermined conditions. And the thermoelectric conversion module 100 is comprised by the thermoelectric conversion element containing the thermoelectric conversion element material 10.
　図１に示すように、本実施形態に係る熱電変換モジュール１００においては、熱電変換素子材料１０ａと熱電変換素子材料１０ｂとは、支持基板１１上に、交互にマトリックス状に配置されている。そして、ｙ方向において、熱電変換素子材料１０ａのアノードと熱電変換素子材料１０ｂのカソードとが、電極１２ｂを介して電気的に接続され、熱電変換素子材料１０ａのカソードと熱電変換素子材料１０ｂのアノードとが、電極１２ｂを介して電気的に接続されている。また、ｙ方向の端部においては、熱電変換素子材料１０ａのアノードとｘ方向に隣接する熱電変換素子材料１０ｂのカソードとが、電極１２ｂを介して電気的に接続されている。 As shown in FIG. 1, in the thermoelectric conversion module 100 according to the present embodiment, the thermoelectric conversion element materials 10 a and the thermoelectric conversion element materials 10 b are alternately arranged in a matrix on the support substrate 11. Then, in the y direction, the anode of the thermoelectric conversion element material 10a and the cathode of the thermoelectric conversion element material 10b are electrically connected via the electrode 12b, and the cathode of the thermoelectric conversion element material 10a and the anode of the thermoelectric conversion element material 10b And are electrically connected via the electrode 12b. Further, at the end in the y direction, the anode of the thermoelectric conversion element material 10a and the cathode of the thermoelectric conversion element material 10b adjacent in the x direction are electrically connected via the electrode 12b.
＜熱電変換素子材料１０＞
　熱電変換モジュール１００に備えられる熱電変換素子材料１０は、Ｎ型のバナジウム酸化物結晶化ガラスを含んで構成されるＮ型の熱電変換素子材料（以下、「Ｎ型材料」という」）１０ａと、Ｐ型のバナジウム酸化物結晶化ガラスを含んで構成されるＰ型の熱電変換素子材料（以下、「Ｐ型材料」という」）１０ｂとを含んで構成されている。このように、Ｎ型材料とＰ型材料とが併用されることで、より大きな起電力が利用可能になっている。また、これらはいずれも断面矩形状であり、Ｎ型材料１０ａとＰ型材料１０ｂとは離間して支持基板１１に配置固定されている。
　以下、「Ｎ型材料１０ａ」と「Ｐ型材料１０ｂ」とをまとめて「熱電変換素子材料１０」と呼称するものとする。 <Thermoelectric conversion element material 10>
The thermoelectric conversion element material 10 included in the thermoelectric conversion module 100 is an N-type thermoelectric conversion element material (hereinafter referred to as “N-type material”) 10 a configured to include N-type vanadium oxide crystallized glass; And P-type thermoelectric conversion element material (hereinafter, referred to as "P-type material") 10b configured to include P-type vanadium oxide crystallized glass. Thus, a larger electromotive force can be used by using the N-type material and the P-type material in combination. In addition, these are all rectangular in cross section, and the N-type material 10 a and the P-type material 10 b are arranged and fixed on the support substrate 11 separately from each other.
Hereinafter, "N-type material 10a" and "P-type material 10b" are collectively referred to as "thermoelectric conversion element material 10".
　Ｎ型材料１０ａは、自由電子を含むＮ型の半導体である。Ｎ型材料１０ａにおいては、高温側で発生する自由電子が低温の方へ移動するようになっている。これにより、Ｎ型材料１０ａを電流が通流可能になっている。また、Ｐ型材料１０ｂは、正孔を含むＰ型の半導体である。Ｐ型材料１０ｂにおいては、含まれる正孔が低温の方へ移動するようになっている。これにより、Ｐ型材料１０ｂを電流が通流可能になっている。熱電変換モジュール１００においては、Ｎ型材料１０ａとＰ型材料１０ｂとが電極１２（後記する）により接続されることにより、発電が行われるようになっている。発電により得られた起電力は、外部負荷２０（抵抗、蓄電池等）において利用されるようになっている。 The N-type material 10 a is an N-type semiconductor containing free electrons. In the N-type material 10a, free electrons generated on the high temperature side move toward the low temperature. As a result, current can flow through the N-type material 10a. The P-type material 10 b is a P-type semiconductor containing holes. In the P-type material 10 b, the contained holes move to a lower temperature. Thus, current can flow through the P-type material 10b. In the thermoelectric conversion module 100, power generation is performed by connecting the N-type material 10a and the P-type material 10b by the electrode 12 (described later). The electromotive force obtained by the power generation is used in the external load 20 (resistor, storage battery, etc.).
　Ｎ型材料１０ａとＰ型材料１０ｂとは、基板１１に固定された電極１２により、交互に直列になって接続されている。具体的には、支持基板１１ａに固定された、電流取出用の負極１２ｃ（電極１２）の端部に、Ｎ型材料１０ａが固定されている。そして、このＮ型材料１０ａは、隣接するＰ型材料１０ｂに対して、支持基板１１ｂに固定された電極１２ｂにより固定されている。さらに、このＰ型材料１０ｂは、前記のＮ型材料１０ａとは別の隣接するＮ型材料１０ａに対して、支持基板１１ａに固定された電極１２ａにより固定されている。そして、他の熱電変換素子材料１０においても同様にしてＮ型材料１０ａとＰ型材料１０ｂとが直列に接続され、電流取出用の正極１２ｄ、及び負極１２ｃから、これらを並列に接続するよりも高い起電力が取り出し可能になっている。 The N-type material 10 a and the P-type material 10 b are alternately connected in series by the electrodes 12 fixed to the substrate 11. Specifically, the N-type material 10a is fixed to the end of the current extraction negative electrode 12c (electrode 12) fixed to the support substrate 11a. The N-type material 10a is fixed to the adjacent P-type material 10b by the electrode 12b fixed to the support substrate 11b. Further, the P-type material 10b is fixed to an adjacent N-type material 10a other than the N-type material 10a by an electrode 12a fixed to a support substrate 11a. Then, similarly to the other thermoelectric conversion element materials 10, the N-type material 10a and the P-type material 10b are connected in series in the same manner, and it is more preferable than connecting the positive electrode 12d and the negative electrode 12c for current extraction in parallel. High electromotive force can be taken out.
　ここで、熱電変換素子材料１０に含まれるバナジウム酸化物結晶化ガラスについて、図２を参照しながら説明する。 Here, the vanadium oxide crystallized glass contained in the thermoelectric conversion element material 10 will be described with reference to FIG.
　図２は、熱電変換素子材料１０に含まれるバナジウム酸化物結晶化ガラスについて、示差熱分析（ＤＴＡ）の昇温過程で得られるグラフである。ＤＴＡ測定は、熱電変換素子材料１０に含まれるバナジウム酸化物結晶化ガラス（対象試料）及びα－アルミナ（参照試料）を用い、大気雰囲気で５Ｋ／ｍｉｎの昇温速度で行った。測定に供した対象試料及び参照試料の量は、それぞれ６５０ｍｇとした。 FIG. 2 is a graph obtained in the temperature rising process of differential thermal analysis (DTA) for the vanadium oxide crystallized glass contained in the thermoelectric conversion element material 10. The DTA measurement was performed using a vanadium oxide crystallized glass (target sample) and α-alumina (reference sample) contained in the thermoelectric conversion element material 10 at a temperature rising rate of 5 K / min in the air atmosphere. The amounts of the target sample and the reference sample used for the measurement were each 650 mg.
　本明細書においては、図２に示す、第１吸熱ピークの開始温度をガラス転移点Ｔg（粘度＝１０13.3ｐｏｉｓｅに相当）、該第１吸熱ピークのピーク温度を屈伏点Ｔd（粘度＝１０11.0ｐｏｉｓｅに相当）、第２吸熱ピークのピーク温度を軟化点Ｔs（粘度＝１０7.65ｐｏｉｓｅに相当）、第１発熱ピークの開始温度を結晶化温度Ｔcと定義する。なお、それぞれの温度は、接線法によって求められる温度とする。そして、本明細書に記載の特性温度（ガラス転移点Ｔg、屈伏点Ｔd、軟化点Ｔs及び結晶化温度Ｔc）は前記の定義に基づくものである。 In this specification, it is shown in FIG. 2, (corresponding to a viscosity = 10 13.3 poise) first glass transition onset temperature of the endothermic peak T g, yield point T d (viscosity peak temperature of the first endothermic peak = corresponds to 10 11.0 poise), it corresponds to the second softening point peak temperature of the endothermic peak T s (viscosity = 10 7.65 poise), defines the starting temperature of the first exothermic peak crystallization temperature T c. In addition, let each temperature be temperature calculated | required by the tangent method. And, the characteristic temperatures (glass transition point T g , yield point T d , softening point T s and crystallization temperature T c ) described in the present specification are based on the above-mentioned definitions.
　熱電変換素子材料１０には、通常は軟化点を有し、結晶化するバナジウム酸化物結晶化ガラスが含まれている。これは、バナジウム酸化物ガラスを軟化点以上、結晶化温度以下で加熱することにより焼成した後、さらに、結晶化温度以上で熱処理することにより、バナジウム酸化物結晶を析出させることで、非晶質と結晶が混在したバナジウム酸化物結晶化ガラス（即ち熱電変換素子材料）とすることが可能である。 The thermoelectric conversion element material 10 contains crystallized vanadium oxide glass which normally has a softening point and is crystallized. This is because the vanadium oxide glass is fired by heating it at a temperature higher than the softening point and lower than the crystallization temperature, and then heat treated at a temperature higher than the crystallization temperature to precipitate vanadium oxide crystals. It is possible to use a vanadium oxide crystallized glass (that is, a thermoelectric conversion element material) in which the crystal and the mixture are mixed.
　本実施形態における熱電変換素子材料１０には、前記のように、バナジウム酸化物結晶化ガラスが含まれている。具体的には、熱電変換素子材料１０には、バナジウム酸化物結晶と、非晶質材料としての非晶質のバナジウム酸化物とが含まれている。ただし、熱電変換素子材料１０に含まれる非晶質材料は非晶質のバナジウム酸化物に何ら限られず、他の材料であってもよい。ただし、比較的低温で軟化流動するため、製造工程が容易になるとともに、熱起電力が発生するという観点から、非晶質材料は非晶質のバナジウム酸化物であることが好ましい。 As described above, the vanadium oxide crystallized glass is contained in the thermoelectric conversion element material 10 in the present embodiment. Specifically, the thermoelectric conversion element material 10 contains a vanadium oxide crystal and an amorphous vanadium oxide as an amorphous material. However, the amorphous material contained in the thermoelectric conversion element material 10 is not limited to amorphous vanadium oxide, and may be another material. However, since the softening flow occurs at a relatively low temperature, the manufacturing process becomes easy, and from the viewpoint of the generation of the thermoelectromotive force, the amorphous material is preferably an amorphous vanadium oxide.
　また、熱電変換素子材料１０には、バナジウム酸化物ガラス以外にも、本発明の効果を著しく損なわない範囲で、任意の材料が含まれていてもよい。 In addition to the vanadium oxide glass, the thermoelectric conversion element material 10 may contain any material as long as the effects of the present invention are not significantly impaired.
　具体的には例えば、Ｎ型素子１０ａには、Ｖ2Ｏ5、ＭxＶ2Ｏ5、Ｍ3Ｆｅ4（ＰＯ4）6、Ｍ2（ＰＯ4）Ｏ、Ｖ2（ＰＯ4）Ｏ、Ｍ2ＣｕＯ4、ＭＡｌ2Ｏ4からなる群より選ばれる少なくとも一種の結晶が含まれていてもよい。ただし、Ｍは、アルミニウム、鉄、ヒ素、アンチモン、ビスマス、タングステン、モリブデン、マンガン、ニッケル、銅、銀、アルカリ金属、アルカリ土類金属のいずれかの金属元素である。また、０＜ｘ＜１である。また、Ｐ型素子１０ｂには、ＶＯ2、Ｖ2Ｏ3からなる群より選ばれる少なくとも一種の結晶が含まれていてもよい。これらの金属酸化物結晶が含まれることにより、熱電変換素子材料１０の電気抵抗を小さくすることができ、電力の出力密度をより向上させることができる。 Specifically, for example, in the N-type element 10a, V 2 O 5 , M x V 2 O 5 , M 3 Fe 4 (PO 4 ) 6 , M 2 (PO 4 ) O, V 2 (PO 4 ) O And at least one crystal selected from the group consisting of M 2 CuO 4 and MAl 2 O 4 . However, M is a metal element of any of aluminum, iron, arsenic, antimony, bismuth, tungsten, molybdenum, manganese, nickel, copper, silver, an alkali metal and an alkaline earth metal. Also, 0 <x <1. In addition, the P-type element 10b may include at least one crystal selected from the group consisting of VO 2 and V 2 O 3 . By including these metal oxide crystals, the electrical resistance of the thermoelectric conversion element material 10 can be reduced, and the power output density can be further improved.
　さらに例えば、熱電変換素子材料１０には、バナジウム酸化物ガラス以外のガラスが含まれていてもよい。バナジウム酸化物ガラス以外のガラスが含まれている場合、熱電変換素子材料１０と電極１２との接合界面に存在する非晶質材料（この点の詳細は、図３を参照しながら後記する）は、非晶質のバナジウム酸化物に限られず、別のガラス材料により構成される非晶質材料でもよい。軟化点を有する別のガラスが含まれる場合、軟化点を有さないバナジウム酸化物ガラスを併用することができる。 Furthermore, for example, the thermoelectric conversion element material 10 may contain glass other than vanadium oxide glass. When glass other than vanadium oxide glass is contained, the amorphous material (this point will be described later with reference to FIG. 3) present at the bonding interface between the thermoelectric conversion element material 10 and the electrode 12 Not limited to amorphous vanadium oxide, it may be an amorphous material composed of another glass material. When another glass having a softening point is included, vanadium oxide glass having no softening point can be used in combination.
　バナジウム酸化物結晶化ガラスを含む熱電変換素子材料１０は、粉末状の非晶質のバナジウム酸化物ガラスを含む例えばペーストを電極１２上に塗布して、熱処理することで作製することができる。この熱処理により、非晶質のバナジウム酸化物ガラスが結晶化して、バナジウム酸化物結晶を含むバナジウム酸化物結晶化ガラスが得られる。ちなみに、得られたバナジウム酸化物結晶の粒界には、通常、非晶質のバナジウム酸化物が残存する。なお、塗布する、粉末状のバナジウム酸化物ガラスには、他の任意の成分を併用することができる。このような成分としては、例えば、ガラスの流動性、熱膨張を制御するためのフィラー等が挙げられる。 The thermoelectric conversion element material 10 containing vanadium oxide crystallized glass can be produced by applying, for example, a paste containing powdered amorphous vanadium oxide glass onto the electrode 12 and heat treating it. By this heat treatment, the amorphous vanadium oxide glass is crystallized to obtain a vanadium oxide crystallized glass containing vanadium oxide crystals. Incidentally, amorphous vanadium oxide usually remains at the grain boundaries of the obtained vanadium oxide crystal. In addition, other arbitrary components can be used together to powder-form vanadium oxide glass to apply | coat. As such a component, for example, the fluidity of glass, a filler for controlling thermal expansion, and the like can be mentioned.
　塗布時の塗布方法は、どのようにしてもよい。例えばプラズマディスプレイパネルのリブ製造で使われる厚膜のドライフィルムレジストを用いることができる。具体的には、熱電変換素子材料１０を形成したい箇所にパターニングしたドライフォトレジストを支持基板１１に載置し、パターニング内に前記ペーストを流し込んで塗布することができる。ドライフィルムレジストは絶縁性で低熱伝導率のため、熱電変換材料作製後に残存しうるドライフィルムレジストの除去が不要になるという利点がある。なお、用いられるフィルムは、薄いフィルムを何枚か重ねて貼りあわせたものでもよい。さらに、ドライフィルムレジストの代わりに、ポリイミド等の高耐熱性の樹脂フィルムを用いることもできる。 The application method at the time of application may be any method. For example, a thick film dry film resist used in the production of a rib of a plasma display panel can be used. Specifically, a dry photoresist patterned at a position where the thermoelectric conversion element material 10 is to be formed can be placed on the support substrate 11, and the paste can be poured into the patterning and applied. The dry film resist is insulating and has a low thermal conductivity, so that there is an advantage that the removal of the dry film resist which may remain after the preparation of the thermoelectric conversion material is unnecessary. In addition, the film to be used may be a thin film laminated and laminated. Furthermore, instead of the dry film resist, a high heat resistant resin film such as polyimide can be used.
＜支持基板１１＞
　支持基板１１は、熱電変換素子材料１０と電極１２とを支持固定するものである。具体的には、熱電変換素子材料１０（１０ａ，１０ｂ）は、電極１２（１２ａ，１２ｂ）が固定された支持基板１１（１１ａ，１１ｂ）により挟まれて形成されている。支持基板１１は、ヒートシンク（図示しない）等に接触される低温側の支持基板１１ａと、加熱ヒータ（図示しない）等に接触される高温側の支持基板１１ｂとにより構成される。 <Support substrate 11>
The support substrate 11 supports and fixes the thermoelectric conversion element material 10 and the electrode 12. Specifically, the thermoelectric conversion element material 10 (10a, 10b) is formed to be sandwiched by the support substrate 11 (11a, 11b) to which the electrode 12 (12a, 12b) is fixed. The support substrate 11 is configured of a low temperature side support substrate 11a in contact with a heat sink (not shown) and the like, and a high temperature side support substrate 11b in contact with a heater (not shown) and the like.
　支持基板１１は、絶縁性の基板により構成されている。ただし、導電性の基板が用いられてもよく、この場合には、導電性基板と電極１１との間に絶縁層が設けられる。さらに、支持基板１１は、例えば熱源からの熱を効率よく発電に利用するため、伝熱性に優れた材料により構成することが好ましい。このような基板としては、例えば、アルミナ、窒化アルミニウム等により構成されるセラミックス基板、酸化物層を有するシリコン基板、金属基板等が挙げられる。さらに、熱電変換モジュール１００を湾曲させて設置する場合には、可撓性に優れた基板（例えば樹脂基板等）を用いることもできる。 The support substrate 11 is made of an insulating substrate. However, a conductive substrate may be used, and in this case, an insulating layer is provided between the conductive substrate and the electrode 11. Furthermore, in order to efficiently use the heat from the heat source for power generation, for example, the support substrate 11 is preferably made of a material excellent in heat conductivity. As such a substrate, for example, a ceramic substrate made of alumina, aluminum nitride or the like, a silicon substrate having an oxide layer, a metal substrate and the like can be mentioned. Furthermore, when the thermoelectric conversion module 100 is installed by being curved, a substrate (for example, a resin substrate or the like) excellent in flexibility can also be used.
＜電極１２＞
　電極１２は、本実施形態においてはパターン形状に構成され、熱電変換素子材料１０（アノードと、隣接するカソード）同士を橋渡しするように接続することで、熱電変換素子材料１０において発生した起電力を外部負荷２０に供給するものである。電極１２は、バナジウム酸化物ガラスと反応しにくいものが用いられる。具体的には例えば、チタン、タングステン、タンタル、クロム、ケイ素、アルミニウム、及び、これらの窒化物、ケイ化物、並びに、これらの合金等が挙げられる。ただし、これらの中で抵抗の大きいものを用いる場合、例えば銅、金等の低抵抗の電極層と前記金属からなる層との二層構造の電極が用いられるようにすることが好ましい。 <Electrode 12>
The electrode 12 is configured in a pattern shape in the present embodiment, and connects the thermoelectric conversion element material 10 (the anode and the adjacent cathode) so as to bridge the electromotive force generated in the thermoelectric conversion element material 10 It supplies the external load 20. As the electrode 12, a material which hardly reacts with the vanadium oxide glass is used. Specifically, examples thereof include titanium, tungsten, tantalum, chromium, silicon, aluminum, and nitrides, silicides thereof, and alloys thereof. However, when using the thing with large resistance among these, it is preferable to make it use the electrode of 2 layer structure of the electrode layer of low resistance, such as copper and gold | metal | money, and the layer which consists of said metal, for example.
　電極１２は、どのような方法で支持基板１１に配置固定されてもよい。例えば、はじめに、金属膜が、蒸着、スパッタ等により支持基板１１上に形成されることができる。次いで、形成された金属膜が、フォトリソグラフィ、エッチング等により所望の形状にパターニングすることで、所望の形状の電極１２が形成される。 The electrodes 12 may be arranged and fixed to the support substrate 11 in any manner. For example, first, a metal film can be formed on the support substrate 11 by vapor deposition, sputtering or the like. Next, the formed metal film is patterned into a desired shape by photolithography, etching or the like to form an electrode 12 with a desired shape.
　さらには、電極１２は、金属ペーストを用い、例えばスクリーン印刷、インクジェット印刷、ディスペンサ等により電極パターンを支持基板１１上に印刷し、焼成することで形成するようにしてもよい。この方法において、支持基板１１上に印刷する際に用いられる金属ペーストとしては、例えば、汎用の金属ペースト、導電性フィラーとバナジウム酸化物ガラスとからなるペースト等が使用可能である。用いられる金属は、例えば銀、銅、アルミニウムが挙げられる。 Furthermore, the electrode 12 may be formed by printing an electrode pattern on the support substrate 11 using, for example, screen printing, inkjet printing, a dispenser, or the like using a metal paste and baking it. In this method, as a metal paste used when printing on the support substrate 11, for example, a general-purpose metal paste, a paste composed of a conductive filler and a vanadium oxide glass, and the like can be used. Examples of the metal used include silver, copper and aluminum.
　ここで、熱電変換素子材料１０と電極１２との接合界面について、説明する。熱電変換素子材料１０と電極１２とは、接合界面の一部に非晶質材料（本実施形態では非晶質のバナジウム酸化物）を含んで接合している。図３を参照しながら、具体的に説明する。 Here, the bonding interface between the thermoelectric conversion element material 10 and the electrode 12 will be described. The thermoelectric conversion element material 10 and the electrode 12 are bonded to a part of the bonding interface by containing an amorphous material (amorphous vanadium oxide in this embodiment). This will be specifically described with reference to FIG.
　図３は、本実施形態に係る熱電変換素子における、電極とバナジウム酸化物結晶化ガラスとの接合界面近傍の（ａ）電子顕微鏡による断面写真及び（ｂ）模式図である。なお、図３（ｂ）において、図示の簡略化のために、熱電変換素子材料１０に含まれる結晶１０１（バナジウム酸化物結晶）の図示を一部省略している。なお、図３は、一例として、チタンからなる電極上にバナジウム酸化物ガラスを塗布して焼成した後、真空中で熱処理を行って、Ｎ型のバナジウム酸化物結晶化ガラスを生成させたものである。 FIG. 3 is (a) a sectional photograph by an electron microscope and (b) a schematic view in the vicinity of the bonding interface between the electrode and the vanadium oxide crystallized glass in the thermoelectric conversion element according to the present embodiment. In addition, in FIG.3 (b), illustration of the crystal | crystallization 101 (vanadium oxide crystal) contained in the thermoelectric conversion element material 10 is partially abbreviate | omitted for the simplification of illustration. As an example, FIG. 3 shows that vanadium oxide glass is coated on an electrode made of titanium and fired, and then heat treatment is performed in vacuum to form N-type vanadium oxide crystallized glass. is there.
　図３に示すように、熱電変換素子材料１０は、多くのバナジウム酸化物結晶１０１を含んで構成されている。しかし、熱電変換素子材料１０と電極１２との接合界面には、バナジウム酸化物の非晶質１０２が存在している。より具体的には、本実施形態においては、熱電変換素子材料１０は、含まれるバナジウム酸化物の非晶質１０２を少なくとも介して、電極１２と接合している。 As shown in FIG. 3, the thermoelectric conversion element material 10 is configured to include a large number of vanadium oxide crystals 101. However, at the bonding interface between the thermoelectric conversion element material 10 and the electrode 12, an amorphous 102 of vanadium oxide is present. More specifically, in the present embodiment, the thermoelectric conversion element material 10 is joined to the electrode 12 at least through the amorphous 102 of the vanadium oxide contained.
　熱電変換素子材料１０は、［２．熱電変換素子の製造方法］において後記するが、例えば非晶質のバナジウム酸化物ガラスを含む層を電極１２上に形成し、その後熱処理することで形成することができる。そこで、本実施形態の熱電変換モジュール１００においては、この熱処理時の加熱条件を制御することで、接合界面に非晶質１０２を存在させることができる。 The thermoelectric conversion element material 10 is [2. Although it mentions later in the manufacturing method of a thermoelectric conversion element, it can form by, for example, forming the layer containing an amorphous vanadium oxide glass on the electrode 12, and heat-processing after that. Therefore, in the thermoelectric conversion module 100 of the present embodiment, the amorphous 102 can be made to exist at the bonding interface by controlling the heating condition at the time of the heat treatment.
　このような、本実施形態によれば、例えばスクリーン印刷、塗布等の低コストプロセスを用いて、従来の方法では困難なことがあった、例えば短エレメント長（高さが例えば０．１ｍｍ程度）等の小型の熱電変換素子材料１０を作製することができる。ここで、出力密度は、通常は、熱電変換効率とともに、熱電変換素子材料に流れる熱量にも比例する。したがって、本実施形態の熱電変換素子材料１０を通過する熱流束を増やすこと、及び、単位面積あたりに小さな熱電変換素子材料１０を高密度に形成させることにより、高出力密度化を図ることができる。また、製造工程でのコストが安いため、発電単価を大幅に低減することができる。 According to this embodiment, it is difficult to use the conventional method, for example, by using a low cost process such as screen printing, coating, etc. For example, short element length (height is about 0.1 mm, for example) And so on can be produced. Here, the output density is generally proportional to the amount of heat flowing through the thermoelectric conversion element material as well as the thermoelectric conversion efficiency. Therefore, high output density can be achieved by increasing the heat flux passing through the thermoelectric conversion element material 10 of the present embodiment and forming the small thermoelectric conversion element material 10 at a high density per unit area. . Moreover, since the cost in a manufacturing process is cheap, the power generation unit price can be reduced significantly.
［２．熱電変換素子の製造方法］
　次に、本実施形態に係る熱電変換素子の製造方法（以下、単に「本実施形態の製造方法」という）を、図面を参照しながら説明する。なお、前記のように、本実施形態の熱電変換素子に含まれる非晶質材料は、非晶質のバナジウム酸化物が好ましい。そこで、以下の説明においては、非晶質材料として、非晶質バナジウム酸化物を例に本実施形態の製造方法を説明する。 [2. Method of manufacturing thermoelectric conversion element]
Next, a method of manufacturing a thermoelectric conversion element according to the present embodiment (hereinafter simply referred to as “the manufacturing method of the present embodiment”) will be described with reference to the drawings. As described above, the amorphous material contained in the thermoelectric conversion element of this embodiment is preferably amorphous vanadium oxide. Therefore, in the following description, the manufacturing method of the present embodiment will be described by using amorphous vanadium oxide as an example of the amorphous material.
　本実施形態の製造方法は、支持基板１１に配置固定された電極１２上に、バナジウム酸化物ガラスを含むバナジウム酸化物ガラス層を形成するガラス層形成工程と、前記ガラス層形成工程において形成されたバナジウム酸化物ガラス層を熱処理し、バナジウム酸化物結晶と非晶質材料（本実施形態では、非晶質のバナジウム酸化物）とを含むバナジウム酸化物結晶化ガラス層を形成するとともに、前記電極との接合界面の少なくとも一部に前記非晶質材料を存在させる熱処理工程と、を含むものである。 The manufacturing method of the present embodiment is formed in the glass layer forming step of forming a vanadium oxide glass layer containing vanadium oxide glass on the electrode 12 disposed and fixed on the support substrate 11 and the glass layer forming step. A vanadium oxide glass layer is heat-treated to form a vanadium oxide crystallized glass layer containing vanadium oxide crystals and an amorphous material (in this embodiment, amorphous vanadium oxide), and And a heat treatment step of causing the amorphous material to exist in at least a part of the bonding interface.
＜ガラス層形成工程＞
　本工程においては、まず、バナジウム酸化物ガラスの粉末をペースト化する。本実施形態においては、この粉末中に、非晶質のバナジウム酸化物ガラスが含まれている。そして、例えばステンシル印刷法、スクリーン印刷法、プラズマディスプレイパネルのリブ製造で使われる厚膜のフィルムレジストを用いたパターニング方法等により、ペーストが電極上に塗布される。これにより、バナジウム酸化物ガラスを含むバナジウム酸化物ガラス層が形成される。 <Glass layer formation process>
In the present step, first, a powder of vanadium oxide glass is made into a paste. In this embodiment, the powder contains amorphous vanadium oxide glass. Then, the paste is applied on the electrode by, for example, a stencil printing method, a screen printing method, or a patterning method using a thick film resist used in rib production of a plasma display panel. Thereby, a vanadium oxide glass layer containing vanadium oxide glass is formed.
　塗布するペーストは、バナジウム酸化物ガラスと溶剤とを通常は含む。さらに、適宜樹脂バインダが含まれていてもよい。含まれるバナジウム酸化物ガラスの粒径は特に制限されないが、塗布時の塗布性を考慮すると、平均粒径として５μｍ以下とすることが好ましい。さらに、含まれる溶剤も特に制限されないが、ブチルカルビトールアセテート及びα－テルピネオールが好ましい。加えて、含まれる樹脂バインダも特に制限されないが、エチルセルロース及びニトロセルロースが好ましい。ただし、溶剤としてα－テルピネオールを用いた場合には、樹脂バインダを用いなくてもよい。 The paste to be applied usually comprises vanadium oxide glass and a solvent. Furthermore, a resin binder may be appropriately contained. The particle size of the vanadium oxide glass to be contained is not particularly limited, but in consideration of the coating property at the time of coating, the average particle size is preferably 5 μm or less. Further, the solvent contained is not particularly limited, but butyl carbitol acetate and α-terpineol are preferable. In addition, the resin binder to be contained is not particularly limited, but ethyl cellulose and nitrocellulose are preferable. However, when α-terpineol is used as the solvent, the resin binder may not be used.
＜熱処理工程＞
　本工程においては、形成されたバナジウム酸化物ガラス層に対して、熱処理が行われる。熱処理の条件は、層内にバナジウム酸化物結晶を析出可能な条件であれば特に制限されず、例えば、まず、ペーストを塗布した基板を４２３Ｋ程度の温度で１０分間乾燥して溶剤を揮発させる。その後、５７３Ｋ程度の温度で３０分間仮焼成してバインダを除去し、ガラスの軟化点Ｔs以上の温度で本焼成することにより、バナジウム酸化物ガラス層が形成される。さらにその後、結晶化温度Ｔｃ以上の温度で熱処理することにより、バナジウム酸化物結晶を含むバナジウム酸化物結晶化ガラスが生成する。ただし、全ての非晶質が結晶化するわけではなく、一部は結晶化せずに残存する。本実施形態においては、非晶質のバナジウム酸化物ガラスを用いているため、非晶質のバナジウム酸化物を介して、電極１２と接合するようになる。 <Heat treatment process>
In this step, heat treatment is performed on the formed vanadium oxide glass layer. The conditions of the heat treatment are not particularly limited as long as vanadium oxide crystals can be precipitated in the layer. For example, first, the substrate coated with the paste is dried at a temperature of about 423 K for 10 minutes to evaporate the solvent. Thereafter, temporary baking is performed at a temperature of about 573 K for 30 minutes to remove the binder, and main baking is performed at a temperature equal to or higher than the softening point Ts of the glass, whereby a vanadium oxide glass layer is formed. Furthermore, by heat treatment at a temperature higher than the crystallization temperature Tc, a vanadium oxide crystallized glass containing vanadium oxide crystals is formed. However, not all the amorphous is crystallized, but a part remains without crystallization. In this embodiment, since the amorphous vanadium oxide glass is used, the electrode 12 is joined via the amorphous vanadium oxide.
　熱処理時の雰囲気は特に制限されないが、Ｎ型のバナジウム酸化物結晶化ガラスを生成させる場合には、例えば大気中、真空中又は不活性ガス（窒素、アルゴン等）雰囲気とすることが好ましい。また、Ｐ型のバナジウム酸化物結晶化ガラスを生成させる場合には、例えば水素ガス雰囲気等の還元性雰囲気とすることが好ましい。還元性雰囲気とすることにより、少なくともバナジウムが３価、４価等の低価数のバナジウム酸化物ＶＯ2またはＶ2Ｏ3を析出させることができる。 The atmosphere during the heat treatment is not particularly limited, but in the case of forming an N-type crystallized vanadium oxide glass, for example, in the air, in vacuum or in an inert gas (nitrogen, argon, etc.) atmosphere is preferable. When P-type vanadium oxide crystallized glass is to be produced, for example, a reducing atmosphere such as a hydrogen gas atmosphere is preferably used. By setting a reducing atmosphere, it is possible to precipitate vanadium oxide VO 2 or V 2 O 3 of low valence such as trivalent or tetravalent at least vanadium.
　軟化点を有さないバナジウム酸化物ガラスを用いる場合には、予め調製したＰ、Ｎ両極性のガラス粉末と、これらのガラス粉末が溶融する温度以下で軟化する別のガラス粉末とを混合し、前記方法により混合ガラス粉末をペースト化して塗布、焼成してもよい。 When using vanadium oxide glass which does not have a softening point, a glass powder of P and N which has been prepared in advance and another glass powder which softens at a temperature at which the glass powder melts are mixed, The mixed glass powder may be made into a paste by the above method, and it may be applied and fired.
　なお、熱電変換モジュール１００の耐久性を向上させるために、対となる２枚の支持基板１１ａ，１１ｂの端部をガラス封着することが好ましい。具体的には、支持基板１１ａ，１１ｂの端部に封着用ガラスペースト（封着用ガラスフリットでもよい）を塗布した後、電気炉中で焼成、封着する。このとき、耐久性及び断熱性向上の観点から、熱電変換モジュール１００内部を真空引きしながら封着することが好ましい。また、荷重をかけながら焼成、封着してもよい。封着用ガラスペーストに用いるガラスとしては制限されないが、熱電変換素子材料１０内のバナジウム酸化物結晶化ガラスが軟化溶融して型崩れしない温度領域で封着可能なガラスを用いることが望ましい。また、封着用のガラスは、耐水性に優れたガラスであることが好ましい。 In order to improve the durability of the thermoelectric conversion module 100, it is preferable to seal the ends of the pair of supporting substrates 11a and 11b with glass. Specifically, a glass paste for sealing (or a glass frit for sealing may be applied) is applied to the end portions of the support substrates 11a and 11b, and then it is fired and sealed in an electric furnace. At this time, it is preferable to seal the inside of the thermoelectric conversion module 100 while evacuating from the viewpoint of improving durability and heat insulation. Moreover, you may bake and seal, applying a load. Although it does not restrict | limit as glass used for the glass paste for sealing, It is desirable to use the glass which can be sealed in the temperature range which the vanadium oxide crystallized glass in the thermoelectric conversion element material 10 softens and melts and loses shape. Moreover, it is preferable that the glass for sealing is a glass excellent in water resistance.
＜その他＞
　本実施形態の製造方法においては、前記の工程以外にも、任意の工程を含めることができる。例えば、一旦、還元雰囲気で熱処理によりＰ型のバナジウム酸化物結晶化ガラスを生成させた後、真空中又は不活性ガス雰囲気で熱処理により、Ｐ型のバナジウム酸化物結晶化ガラスをＮ型のバナジウム酸化物結晶化ガラスに変換することもできる。この場合、真空中又は不活性ガス雰囲気での熱処理により、直接、Ｎ型のバナジウム酸化物結晶化ガラスを生成させた場合に比べ、熱電変換素子材料１０の電気抵抗を低減させることができる。 <Others>
In the manufacturing method of this embodiment, arbitrary processes can be included besides the above-mentioned process. For example, once P-type vanadium oxide crystallized glass is formed by heat treatment in a reducing atmosphere, then P-type vanadium oxide crystallized glass is oxidized to N-type vanadium oxide by heat treatment in vacuum or in an inert gas atmosphere. It can also be converted to crystallized glass. In this case, the electric resistance of the thermoelectric conversion element material 10 can be reduced as compared to the case where N-type vanadium oxide crystallized glass is directly generated by heat treatment in vacuum or in an inert gas atmosphere.
　また、Ｐ型のバナジウム酸化物結晶化ガラスを生成させた後、連続して、新たにＮ型のバナジウム酸化物結晶化ガラスを生成させることもできる。具体的には例えば、支持基板１１上に形成された一部の電極１２上にバナジウム酸化物ガラスを含むペーストを塗布して還元性雰囲気で焼成することにより、Ｐ型のバナジウム酸化物結晶化ガラスを生成させた後、Ｐ型のバナジウム酸化物結晶化ガラスと離間（例えば隣接）する位置に、再度、ペーストを電極上に塗布した後、全体を焼成する。その後、真空中又は不活性ガス雰囲気でガラスの結晶化温度で熱処理を行い、Ｎ型のバナジウム酸化物結晶化ガラスを生成させる。このとき、前記Ｐ型のバナジウム酸化物結晶化ガラスの極性は変化せず、Ｐ型のままである。次に、電極が形成された新たな支持基板をその上に重ね合わせる。このとき、熱電変換素子材料１０の極性が交互になるように、直列に接続されるようにする。その後、ガラスの軟化点Ｔs以上の温度で焼成することで、熱電変換モジュール１００を形成することができる。 In addition, after P-type vanadium oxide crystallized glass is formed, N-type vanadium oxide crystallized glass can be newly formed continuously. Specifically, for example, a paste containing vanadium oxide glass is applied onto a part of the electrodes 12 formed on the support substrate 11 and fired in a reducing atmosphere to obtain P-type vanadium oxide crystallized glass The paste is again applied on the electrode at a position separated (for example, adjacent) to the P-type vanadium oxide crystallized glass, and then the whole is fired. Thereafter, heat treatment is performed at a crystallization temperature of the glass in vacuum or in an inert gas atmosphere to form an N-type vanadium oxide crystallized glass. At this time, the polarity of the P-type vanadium oxide crystallized glass does not change and remains P-type. Next, a new support substrate on which an electrode is formed is superimposed on it. At this time, the thermoelectric conversion element materials 10 are connected in series so that the polarities of the elements 10 alternate. Thereafter, by firing at a softening point T s a temperature above the glass, it is possible to form the thermoelectric conversion module 100.
　さらに、例えば、電極１２ａ上に複数のＮ型のバナジウム酸化物結晶化ガラスを形成させた支持基板１１ａと、電極１２ｂ上にＰ型のバナジウム酸化物結晶化ガラスを形成させた支持基板１１ｂを別々に作製した後、支持基板１１ａ，１１ｂを貼り合せ、熱電変換素子材料１０の極性が交互に直列接続されるようにする。その後、前記同様、ガラスの軟化点Ｔs以上の温度で焼成することで、熱電変換モジュール１００を形成することができる。 Furthermore, for example, the supporting substrate 11a in which a plurality of N-type vanadium oxide crystallized glasses are formed on the electrode 12a, and the supporting substrate 11b in which the P-type vanadium oxide crystallized glass is formed on the electrode 12b are separated. Then, the support substrates 11a and 11b are bonded to each other so that the polarities of the thermoelectric conversion element material 10 are alternately connected in series. Thereafter, the same and fired at the softening point T s temperature above the glass, it is possible to form the thermoelectric conversion module 100.
　また、熱電変換素子材料１０ａと熱電変換素子材料１０ｂとは、同じ材料を用いて、熱処理条件を異なるものとすることで、作製するようにしてもよい。一方で、熱電変換素子材料１０ａと熱電変換素子材料１０ｂとは、異なる材料を用いて、熱処理条件を同じものとすることでも、作製することができる。 Further, the thermoelectric conversion element material 10a and the thermoelectric conversion element material 10b may be manufactured by using the same material but by changing the heat treatment conditions. On the other hand, the thermoelectric conversion element material 10a and the thermoelectric conversion element material 10b can also be manufactured by using different materials and making the heat treatment conditions the same.
　次に、本発明を、実施例を挙げてより詳細に説明する。ただし、本発明は以下の実施例に何ら限定されるものではない。
　なお、以下の記載において、熱電変換素子材料１０の極性（Ｎ型及びＰ型）の判断は、ゼーベック係数測定機を用いて熱電変換素子材料１０のゼーベック係数を測定し、ゼーベック係数の正負に基づいて行った。ゼーベック係数が正であればＰ型であり、ゼーベック係数が負であればＮ型である。 The invention will now be described in more detail by way of examples. However, the present invention is not limited to the following examples.
In the following description, determination of the polarity (N-type and P-type) of the thermoelectric conversion element material 10 is performed by measuring the Seebeck coefficient of the thermoelectric conversion element material 10 using a Seebeck coefficient measuring machine. I went. If the Seebeck coefficient is positive it is P-type, and if the Seebeck coefficient is negative it is N-type.
［１．実施例１：個別に作製されたＮ型及びＰ型の熱電変換素子材料を含む熱電変換モジュールの作製］
＜ペーストの調製＞
　表１に、使用したガラスの原料組成、及び示差熱分析曲線から求めたガラス（ＴＥ１、ＴＥ２、ＥＬ１及びＥＬ２）の特性点（ガラス転移点、屈伏点、軟化点及び結晶化温度）を示す。なお、ＥＬ１は、熱電変換モジュールの端部を封止するための封着用ガラス、ＥＬ２は、支持基板上に設けられる電極を形成するための電極形成用ガラスである。
Figure JPOXMLDOC01-appb-T000001
 [1. Example 1: Preparation of a thermoelectric conversion module containing individually manufactured N-type and P-type thermoelectric conversion element materials]
<Preparation of paste>
Table 1 shows the raw material composition of the glass used, and the characteristic points (glass transition point, deformation point, softening point and crystallization temperature) of the glasses (TE1, TE2, EL1, and EL2) obtained from differential thermal analysis curves. In addition, EL1 is sealing glass for sealing the edge part of a thermoelectric conversion module, EL2 is glass for electrode formation for forming the electrode provided on a support substrate.
Figure JPOXMLDOC01-appb-T000001
　ガラスＴＥ１、ＴＥ２、ＥＬ１及びＥＬ２は、以下のようにして調製した。表１の組成の２００ｇの混合原料粉を白金ルツボに入れ、ＴＥ１ガラス及びＴＥ２ガラスの場合は１３７３Ｋ、ＥＬ１ガラス及びＥＬ２ガラスの場合は１０７３Ｋに加熱した電気炉中で、ガラス溶融物の組成が均一になるように撹拌しながら１時間溶融した。その後、４２３Ｋ～４７５Ｋに加熱しておいたステンレス板上で冷却固化させた。さらに、溶解したガラスをスタンプミル及びジェットミルにより数μｍ程度まで微粉砕した。なお、いずれのガラスも非晶質になっていることをＸ線回折により確認した。 The glasses TE1, TE2, EL1 and EL2 were prepared as follows. The composition of the glass melt is uniform in an electric furnace in which 200 g of the mixed material powder having the composition of Table 1 is put in a platinum crucible and heated to 1373 K for TE1 glass and TE2 glass, and 1073 K for EL1 glass and EL2 glass. The mixture was melted for 1 hour while being stirred. Then, it was cooled and solidified on a stainless steel plate heated to 423K to 475K. Furthermore, the melted glass was pulverized to about several μm by a stamp mill and a jet mill. In addition, it was confirmed by X-ray diffraction that all the glasses were also amorphous.
　次いで、軟化点を有するＴＥ２ガラス粉末に対して、５０質量％のエチルセルロース（ＥＣ）とブチルカルビトールアセテート（ＢＣＡ）との混合溶液（ＥＣのＢＣＡに対する質量比は４％）を配合し、熱電変換素子材料用のガラスペーストＡを調製した。また、電極形成用の導電性ペーストＢを調製した。具体的には、表１に示すＥＬ２ガラス粉末と、ＥＬ２ガラス粉末に対する体積割合が８０％の粒径数μｍの銀粒子とを混合し、これらの混合粉末に対して、５０質量％のエチルセルロース（ＥＣ）とブチルカルビトールアセテート（ＢＣＡ）との混合溶液（ＥＣのＢＣＡに対する重量比は４％）を配合して調製した。 Next, a mixed solution of 50% by mass of ethylcellulose (EC) and butyl carbitol acetate (BCA) (mass ratio of EC to BCA is 4%) is blended with TE2 glass powder having a softening point, and thermoelectric conversion is performed. Glass paste A for device material was prepared. In addition, a conductive paste B for electrode formation was prepared. Specifically, EL2 glass powder shown in Table 1 and silver particles with a particle diameter of several μm having a volume ratio of 80% with respect to the EL2 glass powder are mixed, and 50 mass% of ethyl cellulose ( A mixed solution of EC and butyl carbitol acetate (BCA) (weight ratio of EC to BCA is 4%) was formulated.
　また、上下支持基板同士を封着するためのガラスペーストとして、前記Ｎ型、Ｐ型の結晶化ガラス粉末や前記導電性ペーストのガラス粉末の軟化点よりも低い軟化点を有するＥＬ１ガラス粉末に適量のα－テルピネオール溶剤を添加して、封着用ガラスペーストＣを調製した。 In addition, as a glass paste for sealing upper and lower support substrates, an appropriate amount of EL-glass powder having a softening point lower than the softening point of the N-type and P-type crystallized glass powder or the glass powder of the conductive paste. An α-terpineol solvent was added to prepare a sealing glass paste C.
＜熱電変換モジュール１００の製造工程＞
　熱電変換モジュール１００は、図４に示す方法によって作製した。支持基板としてアルミニウム板を用い、アルマイト処理により片側表面にアルミナ層を形成した、２枚のアルミニウム基板１１ａ，１１ｂを用いた。まず、アルミニウム基板表面に形成されたアルミナ層（図４では図示しない）上に、スクリーン印刷により導電性ペーストＢを塗布した。そして、大気中で４２３Ｋ程度の温度で１０分間乾燥して溶剤を揮発させ、５７３Ｋ程度の温度で３０分間仮焼成してバインダを除去した。その後、ガラス軟化点Ｔs以上である７４０Ｋの温度で３０分間本焼成を行い、図４（ａ）に示す電極１２ａ，１２ｂを形成した。 <Manufacturing process of thermoelectric conversion module 100>
The thermoelectric conversion module 100 was produced by the method shown in FIG. An aluminum plate was used as a supporting substrate, and two aluminum substrates 11a and 11b having an alumina layer formed on one surface by anodizing treatment were used. First, conductive paste B was applied by screen printing on an alumina layer (not shown in FIG. 4) formed on the surface of an aluminum substrate. Then, it was dried in the air at a temperature of about 423 K for 10 minutes to volatilize the solvent, and temporarily baked at a temperature of about 573 K for 30 minutes to remove the binder. Thereafter, at a temperature of 740K is the glass softening point T s or more make this baked for 30 minutes, the electrode 12a shown in FIG. 4 (a), to form 12b.
　次に、図４（ｂ）に示すように、支持基板１１ａ，１１ｂの表面に、パターニングされた熱消失型のドライフィルムレジスト３０１を貼り付けた。フィルムの厚みは、ガラスペーストＡの溶剤等が揮発する量を考慮して、所望の熱電変換モジュールの厚みより少し厚くした。 Next, as shown in FIG. 4B, the patterned heat-dissipation dry film resist 301 was attached to the surfaces of the support substrates 11a and 11b. The thickness of the film was slightly thicker than the desired thickness of the thermoelectric conversion module in consideration of the volatilization amount of the solvent and the like of the glass paste A.
　そして、ドライフィルムレジスト３０１のパターン３０２内に、図４（ｃ）に示すように、ガラスペーストＡ（符号３０３で示される部分）及び封着用ガラスペーストＣ（符号３０４で示される部分）をそれぞれ流し込んだ。ここで、封着用ガラスペーストＣの流し込んだ部分は端部のパターンである。その後、大気中で４２３Ｋ程度の温度で１０分間乾燥して溶剤を揮発させ、５７３Ｋ程度の温度で３０分間仮焼成してバインダを除去した。 Then, as shown in FIG. 4C, the glass paste A (portion indicated by reference numeral 303) and the sealing glass paste C (portion indicated by reference numeral 304) are poured into the pattern 302 of the dry film resist 301. It is. Here, the poured portion of the sealing glass paste C is a pattern of the end. Then, it was dried at a temperature of about 423 K in the air for 10 minutes to volatilize the solvent, and temporarily baked at a temperature of about 573 K for 30 minutes to remove the binder.
　以下の工程においては、支持基板１１ａと支持基板１１ｂとで別々に作業した。まず、支持基板１１ａに関しては、電気炉により、温度８２３Ｋで２時間の大気中熱処理を施した。これにより、支持基板１１ａ（第１の支持基板に相当）上に、０．５ｍｍ×０．５ｍｍ×０．１ｍｍ（高さ）の、Ｎ型のバナジウム酸化物結晶化ガラスを含む熱電変換素子材料１０ａが得られた。また、封着層３０５も併せて得られた。 In the following steps, the support substrate 11a and the support substrate 11b were separately worked. First, the support substrate 11a was subjected to heat treatment in the air at a temperature of 823 K for 2 hours in an electric furnace. Thereby, a thermoelectric conversion element material including N-type vanadium oxide crystallized glass of 0.5 mm × 0.5 mm × 0.1 mm (height) on the support substrate 11a (corresponding to the first support substrate) 10a was obtained. In addition, a sealing layer 305 was also obtained.
　ドライフィルムレジストは熱処理時に消失するため、スクリーン印刷に発生しうる、マスクからペーストを押し出すときに発生するペースト端部（角）の形状崩れがなく、膜厚均一性の優れた熱電変換モジュールを形成することができた。 The dry film resist disappears during heat treatment, so that there is no deformation of the paste end (corner) that occurs when extruding the paste from the mask, which may occur in screen printing, and a thermoelectric conversion module with excellent film thickness uniformity is formed. We were able to.
　得られた熱電変換素子材料１０ａについてＸ線回折を行ったところ、Ｖ2Ｏ5、ＣｕxＶ2Ｏ（０．２６＜ｘ＜０．５５）の他に、Ｆｅ3Ｆｅ4（ＰＯ4）6、Ｃｕ3Ｆｅ4（ＰＯ4）6、Ａｌ2ＣｕＯ4、ＦｅＡｌ2Ｏ4（０＜ｘ＜１）等の結晶が析出していることがわかった。 The obtained thermoelectric conversion element material 10a was subjected to X-ray diffraction, and Fe 3 Fe 4 (PO 4 ) in addition to V 2 O 5 and Cu x V 2 O (0.26 <x <0.55) 6 , it was found that crystals such as Cu 3 Fe 4 (PO 4 ) 6 , Al 2 CuO 4 , FeAl 2 O 4 (0 <x <1) were precipitated.
　次に、支持基板１１ｂに関しては、水素ガスフロー（還元性雰囲気）の電気炉により、温度８２３Ｋで２時間の熱処理を施した。これにより、支持基板１１ｂ（第２の支持基板に相当）上に、０．５ｍｍ×０．５ｍｍ×０．１ｍｍ（高さ）の、Ｐ型のバナジウム酸化物結晶化ガラスを含む熱電変換素子材料１０ｂが得られた。なお、支持基板１１ｂに貼り付けたドライフィルムレジスト３０１が残存していたため、有機溶剤により溶解させて除去した。 Next, with respect to the support substrate 11b, heat treatment was performed for 2 hours at a temperature of 823 K in a hydrogen gas flow (reducing atmosphere) electric furnace. Thus, a thermoelectric conversion element material containing 0.5 mm × 0.5 mm × 0.1 mm (height) of P-type vanadium oxide crystallized glass on the support substrate 11 b (corresponding to the second support substrate) 10b was obtained. In addition, since the dry film resist 301 stuck on the support substrate 11b remained, it was made to melt | dissolve and remove with the organic solvent.
　得られた熱電変換素子材料１０ｂについてＸ線回折を行ったところ、Ｖ2Ｏ3の他に、Ｆｅ2ＰＯ5、Ｆｅ2（ＰＯ4）Ｏ、Ｖ2（ＰＯ4）Ｏ等の結晶が析出していることがわかった。 When X-ray diffraction was performed on the obtained thermoelectric conversion element material 10b, crystals of Fe 2 PO 5 , Fe 2 (PO 4 ) O, V 2 (PO 4 ) O, etc. were precipitated besides V 2 O 3 It turned out that I was doing.
　最後に図４（ｅ）に示すように、Ｎ型の熱電変換素子材料１０ａとＰ型の熱電変換素子材料１０ｂとが交互に直列に接続されるように、支持基板１１ａと支持基板１１ｂとを張り合わせた。そして、真空引きしながら、ＴＥ２ガラスとＥＬ１ガラスの軟化点Ｔs以上の６４０Ｋで３０分間本焼成を行った。これにより、図４（ｆ）に示す熱電変換モジュール１００が得られた。 Finally, as shown in FIG. 4 (e), the supporting substrate 11a and the supporting substrate 11b are connected so that the N-type thermoelectric conversion element material 10a and the P-type thermoelectric conversion element material 10b are alternately connected in series. I put it together. Then, main firing was performed for 30 minutes at 640 K which is equal to or higher than the softening point T s of the TE 2 glass and the EL 1 glass while vacuuming. Thereby, the thermoelectric conversion module 100 shown in FIG. 4F was obtained.
　熱電変換モジュール１００の熱電変換素子材料１０と電極１２との接合界面を、電子顕微鏡を用いて観察した。その結果、バナジウム酸化物結晶が多く観察されたが、接合界面の一部において、非晶質のバナジウム酸化物と電極１２とが接合していることがわかった。これにより、前記したように小型化を図ることができ、高出力密度化を図ることができることがわかった。さらに、発電単価を大幅に低減することができることがわかった。また、熱電変換素子材料１０ａと熱電変換素子材料１０ｂとを別々に作製しているため、不留まりをより良好にすることができた。 The bonding interface between the thermoelectric conversion element material 10 and the electrode 12 of the thermoelectric conversion module 100 was observed using an electron microscope. As a result, many vanadium oxide crystals were observed, but it was found that the amorphous vanadium oxide and the electrode 12 were joined at a part of the joining interface. As a result, it has been found that miniaturization can be achieved as described above, and high output density can be achieved. Furthermore, it turned out that the unit price of power generation can be significantly reduced. Moreover, since the thermoelectric conversion element material 10a and the thermoelectric conversion element material 10b were separately manufactured, the non-staying could be made better.
［２．実施例２：同時に作製されたＮ型及びＰ型の熱電変換素子材料を含む熱電変換モジュールの作製］
　前記の実施例１では、Ｎ型の熱電変換素子材料１０ａとＰ型の熱電変換素子材料１０ｂとを別々に作製したが、実施例２では、Ｎ型の熱電変換素子材料１０ａとＰ型の熱電変換素子材料１０ｂとを連続的に作製した。即ち、はじめにＰ型のバナジウム酸化物結晶化ガラスを含む熱電変換素子材料１０ｂを形成し、その極性を維持した状態で新たに全体を焼成し、Ｎ型のバナジウム酸化物結晶化ガラスを含む熱電変換素子材料１０ａを形成した。
　なお、ガラスペーストＡ、導電性ペーストＢ及び封着用ガラスペーストＣは、実施例１で調製したものと同じものを用いた。 [2. Example 2: Production of a thermoelectric conversion module including N-type and P-type thermoelectric conversion element materials produced simultaneously]
In Example 1 described above, the N-type thermoelectric conversion element material 10 a and the P-type thermoelectric conversion element material 10 b were separately manufactured, but in Example 2, the N-type thermoelectric conversion element material 10 a and the P-type thermoelectric conversion The conversion element material 10b was continuously produced. That is, first, the thermoelectric conversion element material 10b containing P-type vanadium oxide crystallized glass is formed, and the whole is newly fired while maintaining its polarity, and the thermoelectric conversion containing N-type vanadium oxide crystallized glass The element material 10a was formed.
The same glass paste A, conductive paste B and sealing glass paste C as used in Example 1 were used.
＜熱電変換モジュール２００の製造工程＞
　熱電変換モジュール２００は、図５に示す方法によって作製した。 <Manufacturing process of thermoelectric conversion module 200>
The thermoelectric conversion module 200 was produced by the method shown in FIG.
　はじめに、前記した実施例１と同様にして、図５（ｂ）に示す、支持基板１１ａ上に、パターニングされたドライフィルムレジスト３０１を貼り付けた。次いで、ドライフィルムレジスト３０１におけるパターン３０２内に、図５（ｃ）に示すように、１つおきに熱電変換素子用のガラスペーストＡ（符号３０３で示される部分）を流し込んだ。なお、端部には封着用ペーストＣを流し込むため、この時点では何も流し込んでいない。そして、実施例１と同様にしてバインダを除去した。 First, in the same manner as in Example 1 described above, a dry film resist 301 patterned was attached onto a support substrate 11a shown in FIG. 5B. Next, as shown in FIG. 5C, every other glass paste A (portion indicated by reference numeral 303) for the thermoelectric conversion element was poured into the pattern 302 in the dry film resist 301. In addition, since the sealing paste C is poured into the end, nothing is poured at this time. Then, in the same manner as in Example 1, the binder was removed.
　そして、水素ガスフロー（還元性雰囲気）の電気炉により、温度８２３Ｋで２時間の熱処理を施した。これにより、図５（ｄ）に示すように、０．５ｍｍ×０．５ｍｍ×０．１ｍｍ（高さ）の、Ｐ型のバナジウム酸化物結晶化ガラスを含む熱電変換素子材料１０ｂが得られた。 Then, heat treatment was performed at a temperature of 823 K for 2 hours in an electric furnace of hydrogen gas flow (reducing atmosphere). As a result, as shown in FIG. 5 (d), a thermoelectric conversion element material 10 b containing 0.5 mm × 0.5 mm × 0.1 mm (height) of P-type vanadium oxide crystallized glass was obtained. .
　次に、ドライレジストフィルム３０１の残りのパターン３０２内に、熱電変換素子用のガラスペーストＡ（図５（ｅ）中、符号３０３で示される部分）及び封着用ガラスペーストＣ（図５（ｅ）中、符号３０４で示される部分）を流し込んだ。そして、実施例１と同様にしてバインダを除去した。 Next, in the remaining pattern 302 of the dry resist film 301, a glass paste A for a thermoelectric conversion element (a portion indicated by reference numeral 303 in FIG. 5 (e)) and a sealing glass paste C (FIG. 5 (e)) In the middle, a portion indicated by reference numeral 304 was poured. Then, in the same manner as in Example 1, the binder was removed.
　そして、１０-6Ｐａ台の真空電気炉により、温度８２３Ｋで２時間の熱処理を施した。これにより、図５（ｆ）に示すように、支持基板１１ａ上に、０．５ｍｍ×０．５ｍｍ×０．１ｍｍ（高さ）の、Ｎ型のバナジウム酸化物結晶化ガラスを含む熱電変換素子材料１０ａが得られた。また、封着層３０５も併せて得られた。このとき、真空電気路に支持基板１１ａを供しても、既に形成されていたＰ型の熱電変換素子材料１０ｂの極性は変化することなく、熱電変換素子材料１０ｂの極性は維持されていた。なお、残存したドライフィルムレジストを溶剤により溶解して除去した。 Then, heat treatment was performed for 2 hours at a temperature of 823 K in a vacuum electric furnace of 10 -6 Pa or so. As a result, as shown in FIG. 5 (f), a thermoelectric conversion element containing N-type vanadium oxide crystallized glass of 0.5 mm × 0.5 mm × 0.1 mm (height) on the support substrate 11a. Material 10a was obtained. In addition, a sealing layer 305 was also obtained. At this time, even if the support substrate 11a is provided in the vacuum electric path, the polarity of the P-type thermoelectric conversion element material 10b which has already been formed is maintained without changing the polarity of the P-type thermoelectric conversion element material 10b. The remaining dry film resist was dissolved in a solvent and removed.
　最後に図５（ｇ）に示すように、支持基板１１ａと支持基板１１ｂとを張り合わせた。そして、真空引きしながら、ＴＥ２ガラスとＥＬ１ガラスの軟化点Ｔs以上の６４０Ｋで３０分間本焼成を行った。これにより、図５（ｈ）に示す熱電変換モジュール２００が得られた。 Finally, as shown in FIG. 5 (g), the support substrate 11a and the support substrate 11b were pasted together. Then, main firing was performed for 30 minutes at 640 K which is equal to or higher than the softening point T s of the TE 2 glass and the EL 1 glass while vacuuming. Thereby, the thermoelectric conversion module 200 shown in FIG. 5H was obtained.
　前記の実施例１と同様、実施例２においても、熱電変換モジュール２００の熱電変換素子材料１０と電極１２との接合界面を、電子顕微鏡を用いて観察した。その結果、バナジウム酸化物結晶が多く観察されたが、接合界面の一部において実施例１と同様、非晶質のバナジウム酸化物と電極１２とが接合していることがわかった。これにより、前記したように小型化を図ることができ、高出力密度化を図ることができることがわかった。さらに、発電単価を大幅に低減することができることがわかった。また、熱電変換素子材料１０ａ，１０ｂの両方を単一の支持基板１１ａ上で作製するため、支持基板１１ｂを貼り合わせる際の位置決めを容易にすることができた。 As in Example 1 described above, also in Example 2, the bonding interface between the thermoelectric conversion element material 10 of the thermoelectric conversion module 200 and the electrode 12 was observed using an electron microscope. As a result, a large amount of vanadium oxide crystals were observed, but it was found that the amorphous vanadium oxide and the electrode 12 were joined at a part of the joining interface as in Example 1. As a result, it has been found that miniaturization can be achieved as described above, and high output density can be achieved. Furthermore, it turned out that the unit price of power generation can be significantly reduced. In addition, since both of the thermoelectric conversion element materials 10a and 10b are manufactured on a single support substrate 11a, positioning at the time of bonding the support substrate 11b can be facilitated.
［３．実施例３：同時に作製されたＮ型及びＰ型の熱電変換素子材料を含む熱電変換モジュールの作製］
　前記の実施例１や実施例２においては、Ｎ型の熱電変換素子材料１０ａとＰ型の熱電変換素子材料１０ｂとは、いずれも、ガラスペーストＡを用いて形成されている。そこで、実施例３では、Ｎ型の熱電変換素子材料１０ａ用の材料とＰ型の熱電変換素子材料１０ｂ用の材料とを異なるものとし、前記の実施例１と同様の方法により、熱電変換モジュール３００を作製した。 [3. Example 3: Preparation of a thermoelectric conversion module including N-type and P-type thermoelectric conversion element materials simultaneously manufactured]
In Example 1 and Example 2 described above, the N-type thermoelectric conversion element material 10 a and the P-type thermoelectric conversion element material 10 b are both formed using the glass paste A. Therefore, in Example 3, the material for the N-type thermoelectric conversion element material 10a and the material for the P-type thermoelectric conversion element material 10b are different, and a thermoelectric conversion module is manufactured in the same manner as in Example 1 above. Three hundred were prepared.
＜Ｎ型の熱電変換素子用材料のガラスペーストＤ、及び、Ｐ型の熱電変換素子用材料のガラスペーストＥの調製＞
　はじめに、表１に示したＴＥ１ガラスの粉末を１０-5Ｐａ台の真空度の電気炉により、温度８２３Ｋで２時間の熱処理を施した。これにより、Ｎ型のバナジウム酸化物結晶化ガラスの粉末が得られた。以下、この粉末を「Ｎ型ガラス粉末」という。得られたＮ型ガラス粉末についてＸ線回折を行ったところ、Ｖ2Ｏ5、ＣｕxＶ2Ｏ（０．２６　＜ｘ＜０．５５）の他に、Ｆｅ3Ｆｅ4（ＰＯ4）6、Ｃｕ3Ｆｅ4（ＰＯ4）6、Ａｌ2ＣｕＯ4、ＦｅＡｌ2Ｏ4（０＜ｘ＜１）等の結晶が析出していることがわかった。 <Preparation of Glass Paste D of N-Type Thermoelectric Conversion Element Material and Glass Paste E of P-Type Thermoelectric Conversion Element Material>
First, the powder of TE1 glass shown in Table 1 was subjected to heat treatment at a temperature of 823 K for 2 hours in an electric furnace at a degree of vacuum of 10 -5 Pa or so. Thus, a powder of N-type vanadium oxide crystallized glass was obtained. Hereinafter, this powder is referred to as "N-type glass powder". When X-ray diffraction was performed on the obtained N-type glass powder, Fe 3 Fe 4 (PO 4 ) 6 in addition to V 2 O 5 and Cu x V 2 O (0.26 <x <0.55) was obtained. It was found that crystals such as Cu 3 Fe 4 (PO 4 ) 6 , Al 2 CuO 4 , FeAl 2 O 4 (0 <x <1) were precipitated.
　また、ＴＥ１ガラスの粉末を水素ガスフローの電気炉により、温度８２３Ｋで２時間の熱処理を施した。これにより、Ｐ型のバナジウム酸化物結晶化ガラスの粉末が得られた。以下、この粉末を「Ｐ型ガラス粉末」という。得られたＰ型ガラス粉末についてＸ線回折を行ったところ、Ｖ2Ｏ3の他に、Ｆｅ2ＰＯ5、Ｆｅ2（ＰＯ4）Ｏ、Ｖ2（ＰＯ4）Ｏ等の結晶が析出していることがわかった。 Further, the powder of TE1 glass was subjected to heat treatment at a temperature of 823 K for 2 hours in an electric furnace of hydrogen gas flow. Thus, a powder of P-type vanadium oxide crystallized glass was obtained. Hereinafter, this powder is referred to as "P-type glass powder". When X-ray diffraction was performed on the obtained P-type glass powder, in addition to V 2 O 3 , crystals such as Fe 2 PO 5 , Fe 2 (PO 4 ) O, and V 2 (PO 4 ) O were precipitated. I found that.
　Ｎ型ガラス粉末及びＰ型ガラス粉末のそれぞれに対して、表１のＴＥ２ガラスを所定量混合し、熱電変換素子材料１０の材料とした。具体的には、まず、Ｎ型ガラス粉末に対してＴＥ２ガラス粉末を体積比で１０％～２０％混合し、さらに、これらの混合粉末に対して５０質量％のエチルセルロース（ＥＣ）とブチルカルビトールアセテート（ＢＣＡ）との混合溶液（ＥＣのＢＣＡに対する重量比は４％）を配合したガラスペーストＤを調製した。ガラスペーストＤは、Ｎ型の熱電変換素子材料１０ａの材料となる。さらに、Ｐ型ガラス粉末についても同様にして配合を行い、ガラスペーストＥを調製した。ガラスペーストＥは、Ｐ型の熱電変換素子材料１０ｂの材料となる。 A predetermined amount of TE2 glass in Table 1 was mixed with each of the N-type glass powder and the P-type glass powder to obtain a material of the thermoelectric conversion element material 10. Specifically, 10% to 20% by volume of TE2 glass powder is mixed with N-type glass powder, and further, 50% by mass of ethyl cellulose (EC) and butyl carbitol are mixed with these mixed powders. The glass paste D which mix | blended the mixed solution (The weight ratio with respect to BCA of EC is 4%) with acetate (BCA) was prepared. The glass paste D is a material of the N-type thermoelectric conversion element material 10 a. Further, P-type glass powder was similarly compounded to prepare a glass paste E. The glass paste E is a material of the P-type thermoelectric conversion element material 10 b.
＜熱電変換モジュール３００の製造工程＞
　熱電変換モジュール３００は、図６に示す方法によって作製した。 <Manufacturing process of thermoelectric conversion module 300>
The thermoelectric conversion module 300 was produced by the method shown in FIG.
　前記した実施例１と同様にして、図６（ｂ）に示すように、支持基板１１ａ上に、パターニングされたドライフィルムレジスト３０１を貼り付けた。そして、ドライレジストフィルム３０１のパターン３０２内に、図６（ｃ）に示すように、前記のガラスペーストＤ（図６（ｃ）中、符号３０６で示される部分）及びガラスペーストＥ（図６（ｃ）中、符号３０７で示される部分）を交互に流し込んだ。さらに、端部には、実施例１で調製した封着用ガラスペーストＣ（図６（ｃ）中、符号３０４で示される部分）を流し込んだ。 In the same manner as in Example 1 described above, as shown in FIG. 6B, the dry film resist 301 patterned was attached onto the support substrate 11a. Then, in the pattern 302 of the dry resist film 301, as shown in FIG. 6C, the glass paste D (portion indicated by reference numeral 306 in FIG. 6C) and the glass paste E (FIG. 6 (FIG. c) In the middle, a portion indicated by reference numeral 307 is alternately poured. Furthermore, at the end, the sealing glass paste C prepared in Example 1 (the portion indicated by reference numeral 304 in FIG. 6C) was poured.
　その後、大気中で４２３Ｋ程度の温度で１０分間乾燥して溶剤を揮発させ、５７３Ｋ程度の温度で３０分間仮焼成してバインダを除去した。次いで、ＴＥ２ガラスとＥＬ１ガラスの軟化点Ｔs以上の６４０Ｋで３０分間本焼成を行った。これにより、図６（ｄ）に示すように、０．５ｍｍ×０．５ｍｍ×０．１ｍｍ（高さ）の、Ｎ型の熱電変換素子材料１０ａ及びＰ型の熱電変換素子材料１０ｂが形成された。また、併せて、封着層３０５が形成された。 Then, it was dried at a temperature of about 423 K in the air for 10 minutes to volatilize the solvent, and temporarily baked at a temperature of about 573 K for 30 minutes to remove the binder. Subsequently, main baking was performed for 30 minutes at 640 K which is higher than the softening point T s of the TE 2 glass and the EL 1 glass. As a result, as shown in FIG. 6D, an N-type thermoelectric conversion element material 10a and a P-type thermoelectric conversion element material 10b of 0.5 mm × 0.5 mm × 0.1 mm (height) are formed. The In addition, the sealing layer 305 was formed.
　なお、酸化により、Ｐ型の熱電変換素子材料１０ｂの極性がＮ型に変化することをより確実に防止するために、本焼成を真空中又は不活性ガス雰囲気中で行うこともできる。この場合、ドライフィルムレジストが消失せず残存するが、前記のように残存しても構わない。 In addition, in order to prevent the polarity of the P-type thermoelectric conversion element material 10b from being changed to N-type more reliably by oxidation, the main baking can also be performed in vacuum or in an inert gas atmosphere. In this case, the dry film resist does not disappear but remains, but may remain as described above.
　最後に図６（ｅ）に示すように、支持基板１１ａと支持基板１１ｂとを張り合わせた。そして、真空引きしながら、ＴＥ２ガラスとＥＬ１ガラスの軟化点Ｔs以上の６４０Ｋで３０分間本焼成を行った。これにより、図６（ｆ）に示す熱電変換モジュール３００が得られた。 Finally, as shown in FIG. 6 (e), the support substrate 11a and the support substrate 11b were pasted together. Then, main firing was performed for 30 minutes at 640 K, which is equal to or higher than the softening point T s of TE 2 glass and EL 1 glass, while drawing a vacuum. Thereby, the thermoelectric conversion module 300 shown in FIG. 6F was obtained.
　前記の実施例１と同様、実施例３においても、熱電変換モジュール３００の熱電変換素子材料１０と電極１２との接合界面を、電子顕微鏡を用いて観察した。その結果、バナジウム酸化物結晶が多く観察されたが、接合界面の一部において実施例１と同様、非晶質のバナジウム酸化物と電極１２とが接合していることがわかった。これにより、前記したように小型化を図ることができ、高出力密度化を図ることができることがわかった。さらに、発電単価を大幅に低減することができることがわかった。また、熱電変換素子材料１０ａ、１０ｂの両方を単一の支持基板１１ａ上で作製しているため、支持基板１１ｂを貼り合わせる際の位置決めを容易にすることができた。また、一回の熱処理で熱電変換素子材料１０ａ，１０ｂを作製できるため、工程を簡便にすることができた。 As in Example 1 described above, also in Example 3, the bonding interface between the thermoelectric conversion element material 10 of the thermoelectric conversion module 300 and the electrode 12 was observed using an electron microscope. As a result, a large amount of vanadium oxide crystals were observed, but it was found that the amorphous vanadium oxide and the electrode 12 were joined at a part of the joining interface as in Example 1. As a result, it has been found that miniaturization can be achieved as described above, and high output density can be achieved. Furthermore, it turned out that the unit price of power generation can be significantly reduced. In addition, since both of the thermoelectric conversion element materials 10a and 10b are manufactured on the single support substrate 11a, positioning at the time of bonding the support substrate 11b can be facilitated. In addition, since the thermoelectric conversion element materials 10a and 10b can be manufactured by one heat treatment, the process can be simplified.
［４．熱電特性評価］
　実施例１～実施例３において作製した熱電変換モジュール１００，２００，３００は、いずれも、Ｎ型の熱電変換素子材料１０ａ及びＰ型の熱電変換素子材料１０ｂを備えている。そこで、これらの代表として、実施例１において作製した熱電変換モジュール１００について、熱電特性評価を行った。 [4. Thermoelectric property evaluation]
The thermoelectric conversion modules 100, 200, and 300 manufactured in the first to third embodiments each include the N-type thermoelectric conversion element material 10a and the P-type thermoelectric conversion element material 10b. Therefore, as a representative of them, the thermoelectric characteristic evaluation was performed on the thermoelectric conversion module 100 manufactured in the first embodiment.
　実施例１の方法に従って、１０００個のＮ型の熱電変換素子材料１０ａと、１０００個のＰ型の熱電変換素子材料１０ｂとが直列に接続された熱電変換モジュール１００を作製した。そして、作製した熱電変換モジュール１００を、図７に示すように設置した。 According to the method of Example 1, a thermoelectric conversion module 100 in which 1000 N-type thermoelectric conversion element materials 10a and 1000 P-type thermoelectric conversion element materials 10b were connected in series was produced. And the produced thermoelectric conversion module 100 was installed as shown in FIG.
　図７は、実施例１において作製した熱電変換モジュールについての熱電特性評価方法を説明する図である。なお、図７は、構造を把握し易くするために、図１に示した熱電変換モジュール１００の形状から一部変更して記載している。 FIG. 7 is a diagram for explaining a method of evaluating the thermoelectric characteristics of the thermoelectric conversion module manufactured in the first embodiment. In addition, in order to make a structure easy to grasp, FIG. 7 is partially changed and described from the shape of the thermoelectric conversion module 100 shown in FIG.
　熱電変換モジュール１００は銅ブロック７０２上に載置し、熱電変換モジュール１００の上には加熱ヒータ７０１を載置した。銅ブロック７０２は、ヒートシンク７０３に載置されている。従って、加熱ヒータ７０１からの熱は、熱電変換モジュール１００の支持基板１１ｂ側から熱電変換素子材料１０に供給されるようになっている。即ち、支持基板１１ｂ側が高温側になっている。一方で、支持基板１１ａ側は低温側になっている。 The thermoelectric conversion module 100 was placed on the copper block 702, and the heater 701 was placed on the thermoelectric conversion module 100. The copper block 702 is mounted on the heat sink 703. Therefore, the heat from the heater 701 is supplied to the thermoelectric conversion element material 10 from the supporting substrate 11 b side of the thermoelectric conversion module 100. That is, the supporting substrate 11b side is at the high temperature side. On the other hand, the supporting substrate 11a side is at the low temperature side.
　熱電特性の評価は以下のようにして行った。加熱ヒータ７０１の温度を４２３Ｋ（１５０℃）、熱電変換モジュール１００での支持基板１１ａ，１１ｂ間の温度差ΔＴを５０Ｋに設定した。そして、銅ブロック７０２において、熱電変換モジュール１００からヒートシンク７０３方向に流れる熱流束Ｑ，及び、電圧計７０４により測定される出力電圧（起電力）Ｐを測定した。その結果、熱流束Ｑは１０Ｗ／ｃｍ2、出力電圧Ｐは８Ｖであった。さらに、これらの値に基づき、変換効率ηを算出した。ηは、「η＝Ｐ／（Ｑ＋Ｐ）」に基づいて算出した。その結果、変換効率ηは約２％であった。 The evaluation of the thermoelectric characteristics was performed as follows. The temperature of the heater 701 was set to 423 K (150 ° C.), and the temperature difference ΔT between the support substrates 11 a and 11 b in the thermoelectric conversion module 100 was set to 50 K. Then, in the copper block 702, the heat flux Q flowing from the thermoelectric conversion module 100 in the direction of the heat sink 703 and the output voltage (electromotive force) P measured by the voltmeter 704 were measured. As a result, the heat flux Q was 10 W / cm 2 and the output voltage P was 8V. Furthermore, conversion efficiency η was calculated based on these values. η was calculated based on “η = P / (Q + P)”. As a result, the conversion efficiency η was about 2%.
　本実施形態の熱電変換モジュール１００は、熱電変換素子材料１０と電極１２との接合界面において非晶質のバナジウム酸化物ガラス（非晶質材料）を含む熱電変換素子１２を備えている。そのため、前記したように小型化を図ることができ、高出力密度化を図ることができる。さらに、発電単価を大幅に低減することができる。また、本実施例では、Ｐ型及びＮ型で合計２０００個の熱電変換素子材料１０を作製したが、さらなる小型化を図ることで、例えば合計で２万個程度の熱電変換モジュールを作製することもできる。これにより、出力密度をさらに向上させることができるとともに、変換効率をもさらに向上させることができる。 The thermoelectric conversion module 100 according to the present embodiment includes the thermoelectric conversion element 12 including amorphous vanadium oxide glass (amorphous material) at the bonding interface between the thermoelectric conversion element material 10 and the electrode 12. Therefore, as described above, downsizing can be achieved, and high output density can be achieved. Furthermore, the unit price of power generation can be significantly reduced. In addition, in the present embodiment, a total of 2000 thermoelectric conversion element materials 10 of P-type and N-type were manufactured, but by further downsizing, for example, about 20,000 total thermoelectric conversion modules are to be manufactured. You can also. As a result, the output density can be further improved, and the conversion efficiency can be further improved.
１０，１０ａ，１０ｂ　熱電変換素子材料（熱電変換素子）
１１，１１ａ，１１ｂ　支持基板
１２，１２ａ，１２ｂ，１２ｃ　電極（熱電変換素子）
１００　熱電変換モジュール
２００　熱電変換モジュール
３００　熱電変換モジュール 10, 10a, 10b Thermoelectric conversion element material (thermoelectric conversion element)
11, 11a, 11b Supporting substrate 12, 12a, 12b, 12c electrode (thermoelectric conversion element)
100 thermoelectric conversion module 200 thermoelectric conversion module 300 thermoelectric conversion module

Claims (12)

  1. 　支持基板と、
    　前記支持基板に配置され、バナジウム酸化物結晶と非晶質材料とを含むバナジウム酸化物結晶化ガラスを含んで構成される複数の熱電変換素子材料と、
    　前記支持基板に配置され、前記熱電変換素子材料同士を接続するとともに、前記熱電変換素子材料において発生した起電力を消費する外部負荷が接続される電極と、を備え、
    　前記熱電変換素子材料と前記電極とは、前記熱電変換素子材料に含まれる少なくとも前記非晶質材料を介して接合していることを特徴とする、熱電変換モジュール。     A supporting substrate,
    A plurality of thermoelectric conversion element materials disposed on the support substrate and comprising vanadium oxide crystallized glass comprising vanadium oxide crystals and an amorphous material;
    And an electrode connected to an external load which is disposed on the support substrate and connects the thermoelectric conversion element materials to each other and which consumes an electromotive force generated in the thermoelectric conversion element material,
    The thermoelectric conversion module, wherein the thermoelectric conversion element material and the electrode are joined via at least the amorphous material contained in the thermoelectric conversion element material.
  2. 　前記熱電変換素子材料は、Ｎ型のバナジウム酸化物結晶化ガラスを含んで構成されるＮ型の熱電変換素子材料と、前記Ｎ型の熱電変換素子とは離間して配置され、Ｐ型のバナジウム酸化物結晶化ガラスを含んで構成されるＰ型の熱電変換素子材料と、を含むことを特徴とする、請求の範囲第１項に記載の熱電変換モジュール。 In the thermoelectric conversion element material, an N-type thermoelectric conversion element material configured to include N-type vanadium oxide crystallized glass, and the N-type thermoelectric conversion element are disposed apart from each other, and P-type vanadium The P-type thermoelectric conversion element material comprised including oxide crystallization glass, and the thermoelectric conversion module of Claim 1 characterized by the above-mentioned.
  3. 　前記Ｎ型の熱電変換素子材料が、Ｖ2Ｏ5、ＭxＶ2Ｏ5、Ｍ3Ｆｅ4（ＰＯ4）6、Ｍ2（ＰＯ4）Ｏ、Ｖ2（ＰＯ4）Ｏ、Ｍ2ＣｕＯ4、ＭＡｌ2Ｏ4（Ｍは、アルミニウム、鉄、ヒ素, アンチモン、ビスマス、タングステン、モリブデン、マンガン、ニッケル、銅、銀、アルカリ金属、アルカリ土類金属のいずれかの金属元素である。また、０＜ｘ＜１である。）からなる群より選ばれる少なくとも一種の結晶を含んでいることを特徴とする、請求の範囲第２項に記載の熱電変換モジュール。 The N-type thermoelectric conversion element material is V 2 O 5 , M x V 2 O 5 , M 3 Fe 4 (PO 4 ) 6 , M 2 (PO 4 ) O, V 2 (PO 4 ) O, M 2 CuO 4 , MAl 2 O 4 (M is any metal element of aluminum, iron, arsenic, antimony, bismuth, tungsten, molybdenum, manganese, nickel, copper, silver, alkali metal and alkaline earth metal. The thermoelectric conversion module according to claim 2, comprising at least one crystal selected from the group consisting of 0 <x <1).
  4. 　前記Ｐ型の熱電変換素子材料が、ＶＯ2，Ｖ2Ｏ3からなる群より選ばれる少なくとも一種の結晶を含んでいることを特徴とする、請求の範囲第２項又は第３項に記載の熱電変換モジュール。 The P-type thermoelectric conversion element material, characterized in that it contains at least one crystal selected from the group consisting of VO 2, V 2 O 3, according to paragraph 2 or claim 3 Thermoelectric conversion module.
  5. 　支持基板に配置固定された電極上に、バナジウム酸化物ガラスを含むバナジウム酸化物ガラス層を形成するガラス層形成工程と、
    　前記ガラス層形成工程において形成されたバナジウム酸化物ガラス層を熱処理し、バナジウム酸化物結晶と非晶質材料とを含むバナジウム酸化物結晶化ガラス層を形成するとともにに、前記電極との接合界面の少なくとも一部に前記非晶質材料を存在させる熱処理工程と、を含むことを特徴とする、熱電変換モジュールの製造方法。     A glass layer forming step of forming a vanadium oxide glass layer containing vanadium oxide glass on an electrode disposed and fixed to a supporting substrate;
    The vanadium oxide glass layer formed in the glass layer forming step is heat-treated to form a vanadium oxide crystallized glass layer containing vanadium oxide crystals and an amorphous material, and at the bonding interface with the electrode A heat treatment step of causing the amorphous material to exist at least in part, and a method of manufacturing a thermoelectric conversion module.
  6. 　前記熱処理工程は、
    　前記ガラス層形成工程において形成されたバナジウム酸化物ガラス層を熱処理して、Ｎ型のバナジウム酸化物結晶化ガラス層を形成するＮ型結晶析出工程と、
    　前記ガラス層形成工程において形成されたバナジウム酸化物ガラス層を熱処理して、Ｐ型のバナジウム酸化物結晶化ガラス層を形成するＰ型結晶析出工程と、を含むことを特徴とする、請求の範囲第５項に記載の熱電変換モジュールの製造方法。     The heat treatment step is
    N-type crystal precipitation step of heat-treating the vanadium oxide glass layer formed in the glass layer forming step to form an N-type vanadium oxide crystallized glass layer;
    Heat-treating the vanadium oxide glass layer formed in the glass layer forming step to form a P-type vanadium oxide crystallized glass layer, and a P-type crystal precipitation step. The manufacturing method of the thermoelectric conversion module of Claim 5.
  7. 　前記Ｎ型結晶析出工程は、大気中、真空中又は不活性ガス雰囲気で行われることを特徴とする、請求の範囲第６項に記載の熱電変換モジュールの製造方法。 The method for manufacturing a thermoelectric conversion module according to claim 6, wherein the N-type crystal deposition step is performed in the air, in a vacuum or in an inert gas atmosphere.
  8. 　前記Ｐ型結晶析出工程は、還元性雰囲気で行われることを特徴とする、請求の範囲第６項又は第７項に記載の熱電変換モジュールの製造方法。 The method for manufacturing a thermoelectric conversion module according to claim 6, wherein the P-type crystal deposition step is performed in a reducing atmosphere.
  9. 　還元性雰囲気で前記Ｐ型結晶析出工程が行われた後、形成されたＰ型のバナジウム酸化物結晶化ガラスに対して真空中又は不活性ガス雰囲気で熱処理を行って、Ｎ型のバナジウム酸化物結晶化ガラスを形成する前記Ｎ型結晶析出工程が行われることを特徴とする、請求の範囲第６項に記載の熱電変換モジュールの製造方法。 After the P-type crystal precipitation step is performed in a reducing atmosphere, the formed P-type vanadium oxide crystallized glass is heat-treated in vacuum or in an inert gas atmosphere to obtain an N-type vanadium oxide The method for manufacturing a thermoelectric conversion module according to claim 6, wherein the N-type crystal precipitation step of forming a crystallized glass is performed.
  10. 　前記熱処理工程において、前記電極上にＰ型の前記バナジウム酸化物結晶化ガラス層を形成した後、形成された前記Ｐ型のバナジウム酸化物結晶化ガラス層に離間して、前記電極上にバナジウム酸化物ガラス層を形成する第２ガラス層形成工程と、
    　前記第２ガラス層形成工程において形成されたバナジウム酸化物ガラス層を含む前記支持基板全体を熱処理して、前記Ｐ型のバナジウム酸化物結晶化ガラス層の半導体極性を維持したまま、前記バナジウム酸化物ガラス層内にＮ型のバナジウム酸化物結晶化ガラスを生成させる第２熱処理工程と、を含むことを特徴とする、請求の範囲第６項に記載の熱電変換モジュールの製造方法。     In the heat treatment step, the P-type vanadium oxide crystallized glass layer is formed on the electrode, and then the formed P-type vanadium oxide crystallized glass layer is separated to form vanadium oxide on the electrode. A second glass layer forming step of forming a second glass layer;
    The entire supporting substrate including the vanadium oxide glass layer formed in the second glass layer forming step is heat-treated to maintain the semiconductor polarity of the P-type vanadium oxide crystallized glass layer while the vanadium oxide is maintained. 7. A method of manufacturing a thermoelectric conversion module according to claim 6, further comprising: a second heat treatment step of producing N-type vanadium oxide crystallized glass in the glass layer.
  11. 　前記Ｎ型結晶析出工程は、前記支持基板のうちの第１の支持基板を用いて行われ、
    　前記Ｐ型結晶析出工程は、前記支持基板のうちの第２の支持基板に用いて行われ、
    　前記Ｎ型のバナジウム酸化物結晶化ガラス層が形成された前記第１の支持基板と、前記Ｐ型のバナジウム酸化物結晶化ガラス層が形成された前記第２の支持基板とを貼り合わせることにより、熱電変換モジュールを製造することを特徴とする、請求の範囲第６項に記載の熱電変換モジュールの製造方法。     The N-type crystal deposition step is performed using the first support substrate of the support substrates,
    The P-type crystal deposition step is performed using the second support substrate of the support substrates,
    By bonding the first support substrate on which the N-type vanadium oxide crystallized glass layer is formed, and the second support substrate on which the P-type vanadium oxide crystallized glass layer is formed The method for producing a thermoelectric conversion module according to claim 6, wherein the thermoelectric conversion module is produced.
  12. 　請求の範囲第５項又は第６項に記載の製造方法により製造されたことを特徴とする、熱電変換モジュール。 A thermoelectric conversion module manufactured by the manufacturing method according to claim 5 or 6.
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JP2017011166A (en) * 2015-06-24 2017-01-12 リンテック株式会社 Thermoelectric semiconductor composition, and thermoelectric conversion material and method for producing the same
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