JP2017073490A - Method for manufacturing thermoelectric conversion module, and thermoelectric conversion module - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoelectric conversion module and a method for manufacturing a thermoelectric conversion module, which enable the achievement of a larger packing density.SOLUTION: A thermoelectric conversion module 1 comprises a plurality of film-like thermoelectric conversion elements 11 and 13 disposed so that their opposing ends are located on a high-temperature part H and a low-temperature part L determined in a plane on a base material 10 respectively, which are connected in series. The thermoelectric conversion elements 11 and 13 are formed by forming a pattern of a photosensitive resin by photolithography and then, etching a thermoelectric conversion element material located thereunder.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a method for manufacturing a thermoelectric conversion module that generates an electromotive force due to a temperature difference, and a thermoelectric conversion module.

  The thermoelectric conversion element generates an electromotive force due to the Seebeck effect due to a temperature difference between both ends. Examples thereof are described in Patent Documents 1 to 3, usually, a plurality of columnar thermoelectric conversion elements are arranged between the upper substrate and the lower substrate, and these are connected in series to form a module, and the upper substrate and the lower substrate An electromotive force is generated by the temperature difference between the two.

JP 2007-266084 JP 11-330569 A Japanese Unexamined Patent Publication No. 9-16447

  When thermoelectric conversion elements are formed between upper and lower substrates, conventionally, columnar thermoelectric conversion elements are joined by solder (Patent Document 1), or thermoelectric conversion element materials are stacked in a columnar shape using a lift-off method (Patent Document). 2) Columnar thermoelectric conversion elements are formed by plating (Patent Document 3). However, when columnar thermoelectric conversion elements are formed by these methods, there is a limit to element integration, and a small area (volume) is sufficient. There is a need for a thermoelectric conversion module that can generate a large electromotive force.

  In addition, since the conventional thermoelectric conversion module has a columnar thermoelectric conversion element arranged between the upper substrate and the lower substrate, it has a certain thickness and cannot be flexibly bent, and the application scene is limited. . Further, it is necessary to provide wiring between the upper and lower substrates or to dispose an insulating layer, resulting in a complicated structure.

  The present invention has been made in view of the above problems, and an object thereof is to provide a method for manufacturing a thermoelectric conversion module capable of high integration.

  1st invention for solving the subject mentioned above is a pattern of the several thermoelectric conversion element of the film | membrane arrange | positioned so that both ends may each be located in the high temperature part and low temperature part which were defined in the plane on a base material Is formed on a substrate using a photolithography technique. A method for manufacturing a thermoelectric conversion module.

The thermoelectric conversion element is, for example, in accordance with the pattern of the thermoelectric conversion element by applying a thermoelectric conversion element material on a substrate, applying a photosensitive resin on the thermoelectric conversion element material, and exposing and developing. The photosensitive resin pattern is formed, the exposed portion of the thermoelectric conversion element material is removed by etching, and the remaining photosensitive resin is removed.
Or the process of apply | coating the photosensitive resin which contained the thermoelectric conversion element material which is an organic material to the said thermoelectric conversion element on a base material, and the pattern of the said thermoelectric conversion element by exposure and image development of the said photosensitive resin Forming as a pattern.

The thermoelectric conversion element includes, for example, an n-type element and a p-type element. Alternatively, only either an n-type element or a p-type element may be included.
Furthermore, the wiring portion may be formed on the substrate using a photolithography technique.
The substrate is preferably a resin film.

  The second invention is characterized in that a plurality of film-like thermoelectric conversion elements are arranged on the base material so that both end portions are respectively located in the high temperature portion and the low temperature portion defined in the plane on the base material. It is a thermoelectric conversion module.

The thermoelectric conversion element includes, for example, an n-type element and a p-type element. Alternatively, only either an n-type element or a p-type element may be included.
Furthermore, a wiring part may be formed on the base material.
The substrate is preferably a resin film.

  In the present invention, after forming a photosensitive resin pattern by photolithography, a method of etching a thermoelectric element material below the pattern, or a method of forming a photosensitive resin pattern including a thermoelectric conversion element material by photolithography is used. A plurality of film-like thermoelectric conversion elements are formed so that both end portions are located at a high temperature portion and a low temperature portion determined on the plane of the substrate. Thereby, it becomes possible to form and integrate thermoelectric conversion elements in a micron order in a thin thermoelectric conversion module as a whole, and to simplify the structure. As a result, a thermoelectric conversion module having a sufficient electromotive force with a smaller area (volume) can be obtained.

  By forming an n-type element and a p-type element as thermoelectric conversion elements and arranging them in series, it becomes possible to obtain a larger electromotive force, and by using only one of the n-type element and the p-type element , Production costs are reduced and processes are reduced. Further, by forming the wiring portion using a photolithography technique, reliable connection between elements can be achieved. Furthermore, a flexible thermoelectric conversion module is obtained by using a resin film as a substrate.

  The present invention can provide a method for manufacturing a thermoelectric conversion module that can be highly integrated.

The figure which shows the thermoelectric conversion module 1 The figure which shows the manufacturing method of the thermoelectric conversion module 1 The figure which shows the manufacturing method of the thermoelectric conversion module 1 The figure which shows the manufacturing method of the thermoelectric conversion module 1 The figure which shows the state which attached the thermoelectric conversion module 1 to the heat source 100. The figure which shows the thermoelectric conversion module 1a The figure which shows the thermoelectric conversion module 1b The figure which shows the manufacturing method of the thermoelectric conversion module 1b The figure which shows the state which attached the thermoelectric conversion module 1b to the heat source 100. The figure which shows the thermoelectric conversion module 1c

  Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings.

[First Embodiment]
(1. Thermoelectric conversion module 1)
FIG. 1 is a diagram showing a thermoelectric conversion module 1 according to a first embodiment of the present invention. Fig.1 (a) is the figure which looked at the thermoelectric conversion module 1 from the top, FIG.1 (b) is sectional drawing by line AA of Fig.1 (a).

  The thermoelectric conversion module 1 of the present embodiment is a film-like (sheet-like) form in which film-like thermoelectric conversion elements 11 and 13 are formed on a base material 10 using photolithography and etching techniques, and is thin as a whole. Formed.

  In the thermoelectric conversion module 1 of the present embodiment, on the plane on the base material 10, a high-temperature portion H that is to be a high temperature during use and a low-temperature portion L that is a low temperature compared thereto are defined. Corresponding to the low temperature part L, the arrangement and shape of the thermoelectric conversion elements 11 and 13 are determined.

  For the substrate 10, a film made of a resin such as polyethylene or polyimide is used. However, the present invention is not limited to this. For example, glass or the like can be used. However, when a resin film is used, there is an advantage that the flexibility is excellent and the application range is wide.

  The thermoelectric conversion element 11 is an n-type element, and when there is a temperature difference between both ends, a current flows from the low temperature end to the high temperature end. In the present embodiment, ITO (indium tin oxide) is used as the thermoelectric conversion element 11, but is not limited thereto. Known inorganic materials that can be used as n-type elements can be used, and examples thereof include platinum, constantan, alumel, SUS (stainless steel), invar, and indium zinc oxide.

  On the other hand, the thermoelectric conversion element 13 is a p-type element, and when there is a temperature difference between both ends, a current flows from a high temperature end to a low temperature end. In the present embodiment, copper is used as the thermoelectric conversion element 13, but is not limited thereto. Known inorganic materials that can be used as p-type elements can be used, examples of which include silver, gold, iron, and chromel.

  In this embodiment, the high temperature part H and the low temperature part L are made into a substantially rectangular area, and the two high temperature parts H and the low temperature parts L are alternately arranged in parallel at intervals. However, the pattern of the high temperature part H and the low temperature part L is not restricted to this.

  The thermoelectric conversion elements 11 and 13 are arranged in two upper and lower rows, and in each row, the two ends of the plane are arranged in the high temperature portion H and the low temperature portion L, respectively.

  The thermoelectric conversion elements 13 have a stripe shape, and in each row, a plurality of thermoelectric conversion elements 13 are arranged in parallel at intervals in the longitudinal direction of the high temperature portion H (low temperature portion L).

  The thermoelectric conversion elements 11 are arranged so as to connect adjacent thermoelectric conversion elements 13 in each row. That is, the thermoelectric conversion element 11 is disposed so as to connect the end portion on the low temperature portion L side of one thermoelectric conversion element 13 and the end portion on the high temperature portion H side of the other thermoelectric conversion element 13.

  A wiring portion 15 is also provided on the substrate 10. The wiring part 15 can use various conductive materials, for example, can use copper, silver, gold | metal | money, aluminum, etc.

  In the present embodiment, one of the thermoelectric conversion elements 11 (the upper element in the figure) among the thermoelectric conversion elements 11 (the upper and lower two thermoelectric conversion elements 11 at the left end in FIG. 1A) at the end of each row. A circuit in which the end on the part H side and the end on the low-temperature part L side of the other thermoelectric conversion element 11 (lower element in the figure) are connected by the wiring part 15 and the thermoelectric conversion elements 11 and 13 are connected in series. Is formed on the substrate 10. Also, wiring portions 15 are provided at both ends of the circuit.

  In the thermoelectric conversion module 1, the protective layer 17 is provided so as to cover the thermoelectric conversion elements 11 and 13 and the wiring part 15 on the base material 10. The protective layer 17 is formed into a thin film by bonding various known resin films or applying a resin. In addition, illustration of the protective layer 17 is abbreviate | omitted in Fig.1 (a). The same applies to FIG. 6A, FIG. 7A, and FIG.

(2. Manufacturing method of thermoelectric conversion module 1)
As described above, in the present embodiment, when the thermoelectric conversion module 1 is manufactured, the thermoelectric conversion elements 11 and 13 are formed on the base material 10 by using photolithography and etching techniques.

  That is, first, as shown in FIG. 2 (a), ITO, which is a material of the thermoelectric conversion element 11 (thermoelectric conversion element material), is applied on the base material 10 by sputtering, vapor deposition, or the like. As shown, a photosensitive resin 21 (resist) is applied. In this embodiment, the photosensitive resin 21 is a positive type, and the photosensitive resin 21 at the location is softened by exposing a location other than the pattern of the thermoelectric conversion element 11.

  By performing the development, as shown in FIG. 2C, the photosensitive resin 21 at the corresponding portion is removed, and a pattern of the photosensitive resin 21 corresponding to the pattern of the thermoelectric conversion element 11 is formed. The ITO is exposed at the place where the photosensitive resin 21 is removed.

  Thereafter, when etching with an etchant is performed, the exposed portions of ITO are removed as shown in FIG. When the remaining photosensitive resin 21 is removed by chemical treatment or the like, the pattern of the thermoelectric conversion element 11 made of ITO remains as shown in FIG. In addition, as the photosensitive resin 21, a negative type can also be used. In this case, a portion corresponding to the pattern of the thermoelectric conversion element 11 is exposed at the time of exposure.

  In this embodiment, the pattern of the thermoelectric conversion element 11 is thus formed on the substrate 10 as shown in FIG. Similarly, a pattern of the wiring portion 15 is also formed by photolithography and etching as shown in FIG.

  The thermoelectric conversion element 13 is similarly subjected to photolithography and etching, whereby the pattern of the thermoelectric conversion element 13 is formed as shown in FIG. FIG. 4B shows a cross section similar to FIG. 1B at this time. Thereafter, when the protective layer 17 is formed by adhesion or application, the thermoelectric conversion module 1 described in FIG. 1 is obtained.

  As shown in FIG. 5, the thermoelectric conversion module 1 attaches the high temperature part H to various heat sources 100 such as pipes and electronic devices, and bends the base material 10 so that the low temperature part L is separated from the heat source 100. Therefore, it functions as a battery that generates an electromotive force, and can be used as a power source for various sensors, for example.

  As described above, according to the present embodiment, after the pattern of the photosensitive resin 21 is formed by photolithography, the method of etching the thermoelectric element material below the pattern is defined on the plane of the base material 10. A plurality of film-like thermoelectric conversion elements 11 and 13 are formed so that both ends are positioned at the high temperature portion H and the low temperature portion L. As a result, the thermoelectric conversion elements 11 and 13 can be formed and integrated in a micron order in the thin thermoelectric conversion module 1 as a whole, and the structure can be simplified. As a result, the thermoelectric conversion module 1 having a sufficient electromotive force with a smaller area (volume) can be obtained.

  Further, an n-type element and a p-type element are formed as the thermoelectric conversion elements 11 and 13, and a larger electromotive force can be obtained by arranging them in series. Note that a circuit in which series and parallel patterns are combined may be used depending on the design.

  Further, by forming the wiring portion 15 using a photolithography technique, reliable connection between elements can be achieved, and the degree of freedom in circuit formation is increased. Furthermore, the flexible thermoelectric conversion module 1 is obtained by using a resin film as the base material 10.

  However, the present invention is not limited to this. Hereinafter, other examples of the present invention will be described as second to fourth embodiments. Each embodiment mainly describes a different configuration from the first embodiment, and the same configuration is denoted by the same reference numeral in the drawings and the like, and the description thereof is omitted.

[Second Embodiment]
FIG. 6 is a diagram showing a thermoelectric conversion module 1a according to the second embodiment. 6A is a view of the thermoelectric conversion module 1a as viewed from above, and FIG. 6B is a cross-sectional view taken along line BB in FIG. 6A.

  In the second embodiment, the thermoelectric conversion elements 11 have the same stripe shape as the thermoelectric conversion elements 13, and the thermoelectric conversion elements 11 and the thermoelectric conversion elements 13 are alternately arranged in parallel in the upper and lower rows. In the present embodiment, the ends on the high temperature part H side or the low temperature part L side of the thermoelectric conversion elements 11 and 13 adjacent in each row are connected by the wiring part 15.

  The thermoelectric conversion module 1a of the second embodiment can be manufactured in the same manner as in the first embodiment, and the same effect as in the first embodiment can be obtained. However, in the present embodiment, unlike the first embodiment, the wiring portion 15 is first formed, and the thermoelectric conversion elements 11 and 13 are formed thereon. Thus, the formation order of the thermoelectric conversion elements 11 and 13 and the wiring part 15 is not specifically limited. Moreover, in 2nd Embodiment, there exists an advantage which can connect the edge part of the adjacent thermoelectric conversion elements 11 and 13 by the wiring part 15 reliably.

[Third Embodiment]
(1. Thermoelectric conversion module 1b)
FIG. 7 is a view showing a thermoelectric conversion module 1b according to the third embodiment. Fig.7 (a) is the figure which looked at the thermoelectric conversion module 1b from the top, and FIG.7 (b) is sectional drawing by line CC of Fig.7 (a).

  The third embodiment is mainly different from the first embodiment in that only the p-type thermoelectric conversion element 13a is used as the thermoelectric conversion element. Moreover, in the thermoelectric conversion module 1b, the two high temperature parts H are closely arranged in parallel, and the two low temperature parts L are arranged in parallel on both sides thereof.

  The thermoelectric conversion elements 13a are arranged in two upper and lower rows, and in each row, the two ends of the plane are arranged in the high temperature portion H and the low temperature portion L, respectively. The thermoelectric conversion elements 13a have a stripe shape, and a plurality of thermoelectric conversion elements 13a are arranged in parallel at intervals in the longitudinal direction of the high temperature portion H (low temperature portion L) in each row.

  In the adjacent thermoelectric conversion elements 13a in each row, the end on the low temperature part L side of one thermoelectric conversion element 13a and the end on the high temperature part H side of the other thermoelectric conversion element 13a are connected by the wiring part 15.

  Of the thermoelectric conversion elements 13a at the end of each row (upper and lower two thermoelectric conversion elements 13a in FIG. 7A), one end of the thermoelectric conversion element 13a (the upper element in the figure) on the low temperature part L side And the other thermoelectric conversion element 13a (element on the lower side of the drawing) on the high temperature part H side are connected by the wiring part 15, and a circuit in which the thermoelectric conversion elements 13a are connected in series is formed on the substrate 10. Is done. Note that both ends of the circuit are wiring portions 15.

(2. Manufacturing method of thermoelectric conversion module 1b)
The thermoelectric conversion element 13a can be formed in the same manner as in the first embodiment, but in this embodiment, PEDOT: PSS (polystyrene sulfonic acid (PSS) -added polyethylene is used as the material of the thermoelectric conversion element 13a (thermoelectric conversion element material). Using a conductive polymer material (organic material) such as dioxythiophene (PEDOT), a pattern of a plurality of film-like thermoelectric conversion elements 13a is formed by a photolithography technique.

  That is, in this embodiment, as shown in FIG. 8A, after forming the pattern of the wiring portion 15 on the base material 10 by the same method as in the first embodiment, as shown in FIG. A negative photosensitive resin containing PEDOT: PSS, which is a material of the thermoelectric conversion element 13a, is applied.

  Thereafter, the portion corresponding to the pattern of the thermoelectric conversion element 13a is cured by exposure, and the other portions are removed by development, whereby the pattern of the thermoelectric conversion element 13a becomes a pattern of a photosensitive resin as shown in FIG. Formed as. Thereafter, when the protective layer 17 is formed by adhesion or application, the thermoelectric conversion module 1b described in FIG. 7 is obtained.

  The organic material used in this embodiment is not particularly limited as long as it can be used as a thermoelectric conversion element, and the photosensitive resin is not particularly limited. Further, a positive type resin can be used as the photosensitive resin, and in this case, portions other than the pattern of the thermoelectric conversion element 13a are exposed at the time of exposure.

  As shown in FIG. 9, the thermoelectric conversion module 1 b attaches two adjacent high-temperature parts H to the heat source 100, and bends the base material 10 so that the low-temperature parts L on both sides are separated from the heat source 100, thereby generating an electromotive force. It can function as a battery that generates It is also possible to make the substrate 10 easier to bend by providing a cut or the like.

  In the third embodiment, the same effect as in the first embodiment can be obtained. Further, since one type of thermoelectric conversion element 13a is used, costs such as material costs can be suppressed and the number of processes is reduced.

  In this embodiment, only the p-type thermoelectric conversion element is used, but only the n-type thermoelectric conversion element may be used instead. Further, when n-type and p-type thermoelectric conversion elements are used as in the first embodiment, both thermoelectric conversion elements can be formed by photolithography as in this embodiment using an organic material. Alternatively, one thermoelectric conversion element is formed by photolithography using an organic material as in the present embodiment, and the other is formed by using photolithography and etching techniques using an inorganic material as in the first embodiment. It is also possible to do.

[Fourth Embodiment]
Fig.10 (a) is the figure which looked at the thermoelectric conversion module 1c which concerns on 4th Embodiment from the top. In the fourth embodiment, the base material 10 is circular, and concentric high-temperature parts H and low-temperature parts L are defined in the center part and the outer peripheral part.

  A plurality of thermoelectric conversion elements 11 and 13 are arranged radially from the center of the substrate 10 toward the outer periphery, and both end portions are located in the high temperature portion H and the low temperature portion L. The thermoelectric conversion elements 11 and 13 are alternately arranged in the circumferential direction of the base material 10 at intervals, and the ends of the adjacent thermoelectric conversion elements 11 and 13 on the high temperature part H side or the low temperature part L side are connected by the wiring part 15. By connecting, a series circuit is formed.

  For example, as shown in FIG. 10B, the thermoelectric conversion module 1c is a battery that generates an electromotive force by attaching a high temperature portion H to the bottom surface of the heat source 100 ′ and disposing the low temperature portion L away from the heat source 100 ′. Function.

  In the fourth embodiment, the same effect as in the first embodiment can be obtained. As described above, the shape and the wiring pattern of the thermoelectric conversion module can be variously determined according to the intended usage and the like.

  The preferred embodiments of the present invention have been described above with reference to the accompanying drawings, but the present invention is not limited to such examples. It will be apparent to those skilled in the art that various changes or modifications can be conceived within the scope of the technical idea disclosed in the present application, and these are naturally within the technical scope of the present invention. Understood.

1, 1a, 1b, 1c, 1d; thermoelectric conversion module 10; base material 11, 13, 13a; thermoelectric conversion element 15; wiring portion 17; protective layer 100, 100 ';

Claims (12)

A pattern of a plurality of film-like thermoelectric conversion elements arranged so that both end portions are respectively located at a high temperature portion and a low temperature portion determined in a plane on the substrate,
A method for producing a thermoelectric conversion module, which is formed on a substrate using a photolithography technique. The thermoelectric conversion element,
Applying a thermoelectric conversion element material on a substrate;
Applying a photosensitive resin on the thermoelectric conversion element material;
Forming a pattern of the photosensitive resin according to the pattern of the thermoelectric conversion element by exposure and development;
Removing the exposed portion of the thermoelectric conversion element material by etching;
Removing the remaining photosensitive resin;
The thermoelectric conversion module manufacturing method according to claim 1, wherein the thermoelectric conversion module is formed by: The thermoelectric conversion element,
Applying a photosensitive resin containing a thermoelectric conversion element material that is an organic material on a base material;
Forming a pattern of the thermoelectric conversion element as a pattern of the photosensitive resin by exposure and development; and
The thermoelectric conversion module manufacturing method according to claim 1, wherein the thermoelectric conversion module is formed by:   The said thermoelectric conversion element contains an n-type element and a p-type element, The manufacturing method of the thermoelectric conversion module in any one of Claims 1-3 characterized by the above-mentioned.   The said thermoelectric conversion element contains only either an n-type element or a p-type element, The manufacturing method of the thermoelectric conversion module in any one of Claims 1-3 characterized by the above-mentioned.   The method for manufacturing a thermoelectric conversion module according to claim 1, wherein the wiring portion is formed on the base material using a photolithography technique.   The method for manufacturing a thermoelectric conversion module according to claim 1, wherein the base material is a resin film.   A thermoelectric conversion module, wherein a plurality of film-like thermoelectric conversion elements are arranged on a base material such that both end portions are respectively positioned at a high temperature portion and a low temperature portion defined on a plane on the base material.   The thermoelectric conversion module according to claim 8, wherein the thermoelectric conversion element includes an n-type element and a p-type element.   The thermoelectric conversion module according to claim 8, wherein the thermoelectric conversion element includes only one of an n-type element and a p-type element.   The thermoelectric conversion module according to claim 8, wherein a wiring portion is formed on the base material.   The thermoelectric conversion module according to claim 8, wherein the base material is a resin film.

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