JP5056544B2 - Thermoelectric module - Google Patents

Description

  The present invention relates to a thermoelectric module that can be used for thermoelectric power generation and the like.

  In recent years, thermoelectric power generation using the Seebeck effect has been widely used. Thermoelectric power generation is performed by generating an electromotive force by giving a temperature difference to both sides of the thermoelectric element. As materials for thermoelectric elements, n-type thermoelectric semiconductors and p-type thermoelectric semiconductors are known.

  Since the electromotive force of a single thermoelectric element is small, it is necessary to combine a plurality of thermoelectric elements into a module for power generation. When the thermoelectric element is modularized, wiring is facilitated by setting one of the heat source facing surfaces of adjacent thermoelectric elements facing a heat source from one direction as a positive electrode and the other as a negative electrode.

Therefore, conventionally, as shown in Patent Document 1 below, a thermoelectric module in which n-type thermoelectric semiconductors and p-type thermoelectric semiconductors are alternately arranged and combined has been proposed. However, in such a conventional thermoelectric module, it is necessary to laminate an n-type thermoelectric semiconductor and a p-type thermoelectric semiconductor and fire them at the same time, but these semiconductors are made of different materials and have different heat shrinkage rates during firing. Therefore, cracks and peeling occur, and it is difficult to actually manufacture.
JP-A-11-121815

  The present invention has been made in view of such a situation, and an object thereof is to provide a thermoelectric module that is easy to manufacture for integration, high quality, and high reliability.

In order to achieve the above object, the thermoelectric module according to the first aspect of the present invention provides:
A plurality of semiconductor elements of the same conductivity type and having a thermoelectric effect;
A high resistance layer integrally formed at the junction of adjacent semiconductor elements;
A thermoelectric module having a conductor layer integrally formed inside the high-resistance layer and electrically connecting the first end and the second end of adjacent semiconductor elements,
The conductor layer is a mixed layer of a first component made of metal and a second component made of a component constituting the high resistance layer.

The thermoelectric module according to the second aspect of the present invention is:
A plurality of semiconductor elements of the same conductivity type and having a thermoelectric effect;
A high resistance layer integrally formed at the junction of adjacent semiconductor elements;
A thermoelectric module having a conductor layer integrally formed inside the high-resistance layer and electrically connecting the first end and the second end of adjacent semiconductor elements,
The conductor layer is a mixed layer of a first component made of metal and a third component made of a component constituting the semiconductor element.

  Since the thermoelectric module according to the present invention is modularized using a plurality of semiconductor elements having the same conductivity type and thermoelectric effect, manufacturing for integration is facilitated, and cracking or peeling may occur during simultaneous firing. Less. Therefore, the quality of the thermoelectric module is improved and the reliability is improved.

  In the thermoelectric module according to the present invention, the conductor layer located inside the high resistance layer has the first component made of metal and the second component made up of the component making up the high resistance layer, or the component making up the semiconductor element. The 3rd component which consists of is included. For this reason, even at the time of simultaneous firing, the bonding at the interface between the conductor layer and the high resistance layer is improved, and the bonding between the conductor layer and the semiconductor element is also improved, and the occurrence of cracks and the like based on the difference in thermal expansion is caused. It can be reduced.

  Furthermore, in the thermoelectric module according to the present invention, since the conductor layer located inside the high resistance layer contains the second component or the third component together with the first component, the heat insulation of the conductor layer is low. Improved compared to a conductor layer made of only metal. In the thermoelectric module according to the present invention, since the conductor layer extends from the high heat side to the low temperature side with respect to the heat source, the thermoelectric efficiency is improved by improving the thermal insulation.

  In the present invention, the conductor layer may be a mixed layer of the first component, the second component, and the third component.

  Preferably, in the conductor layer, the second component or the third component or both of them are dispersed in a matrix of the first component in which the first component is three-dimensionally connected and connected. . According to the conductor layer having such a structure, the thermal insulation is improved while electrical conduction of the conductor layer is achieved.

  Preferably, the main component of the semiconductor element and the main component of the high resistance layer are common. Since these main components are common, manufacturing for integration is facilitated, and the risk of cracks and peeling during cofiring is reduced.

  Preferably, the main component of the semiconductor element and the main component of the high resistance layer both contain Mn and Ca. By making Mn and Ca the main components and changing their content ratios and changing the composition of the additive, it is possible to make a semiconductor element and a high resistance layer separately.

  Preferably, the width of the conductor layer is narrower than the width of the high resistance layer, and the width of the high resistance layer is equal to or less than the width of the semiconductor element. With such a configuration, short-circuit failure due to the conductor layer can be prevented, and the conductor layer is protected by the high-resistance layer and is not easily oxidized, thereby improving the reliability.

  Preferably, a first terminal portion and a second terminal portion connected to the first end portion and the second end portion of adjacent semiconductor elements are formed at both ends of the conductor layer. The high resistance layer may cover the periphery other than the end face of the semiconductor element to which the first terminal portion and the second terminal portion are connected. Alternatively, the high resistance layer may cover the entire periphery other than the connection portion of the semiconductor element to which the first terminal portion and the second terminal portion are connected. At least the high resistance layer is integrally formed at the junction of the semiconductor element with the conductor layer interposed.

  Each semiconductor element may have a quadrangular prism shape, and both ends of the quadrangular prism may be the first end and the second end, and these semiconductor elements may be arranged in a matrix.

  Alternatively, each semiconductor element has a ring-divided piece shape, and an inner peripheral side and an outer peripheral side of the ring-divided piece are the first end part and the second end part, and these semiconductor elements are at least a part of the ring. May be arranged to form.

  Preferably, the semiconductor element, the high resistance layer, and the conductor layer are formed by sheet molding or printing, and are integrated by simultaneous firing.

  In the present invention, the high resistance layer means a resistance layer having an electrical resistivity at room temperature (25 ° C.) of 500 Ω · cm or more, preferably 1000 Ω · cm or more. In the present invention, the conductor layer refers to a conductive layer having an electrical resistivity at room temperature (25 ° C.) of 0.1 Ω · cm or less, preferably 0.01 Ω · cm or less. Furthermore, in the present invention, the end portion includes not only the end surface but also a side surface located near the end surface.

Hereinafter, the present invention will be described based on embodiments shown in the drawings.
FIG. 1 is a schematic cross-sectional view of a thermoelectric module according to an embodiment of the present invention.
2 (A) to 2 (C) are main part cross-sectional views showing an example of the manufacturing process of the thermoelectric module shown in FIG.
3 (A) to 3 (C) are main part sectional views showing another example of the manufacturing process of the thermoelectric module shown in FIG.
4 (A) to 4 (D) are main part cross-sectional views showing other examples of the manufacturing process according to a modification of the thermoelectric module shown in FIG.
FIG. 5 is a schematic cross-sectional view of a thermoelectric module according to another embodiment of the present invention.
6 (A) to 6 (F) are main part cross-sectional views showing an example of the manufacturing process of the thermoelectric module shown in FIG.
7 (A) to 7 (F) are main part cross-sectional views showing other examples of the manufacturing process of the thermoelectric module shown in FIG.
8 (A) and 8 (B) are main part sectional views showing another example of the manufacturing process of the thermoelectric module shown in FIG.
FIG. 9 is a schematic perspective view of a thermoelectric module according to still another embodiment of the present invention.
10 to 12 are schematic cross-sectional views of thermoelectric modules according to still other embodiments of the present invention.
First embodiment

  As shown in FIG. 1, a thermoelectric module 2 according to an embodiment of the present invention has a plurality of semiconductor elements 4. The semiconductor elements 4 are all semiconductor elements of the same conductivity type, and are n-type or p-type semiconductor elements. The material of the semiconductor element 4 will be described later.

  In this embodiment, each semiconductor element 4 has a quadrangular prism shape extending in the Z-axis direction, and the first end 4a, which is the lower end portion in the Z-axis direction of the quadrangular column, is disposed on the heat source side, The second end 4b, which is the upper end in the Z-axis direction, is on the counter heat source side. That is, a temperature difference is generated between the first end 4 a and the second end 4 b of each semiconductor element 4.

  High resistance layers 6 are formed on the four side surfaces of the semiconductor element 4 having a quadrangular prism shape. The material of the high resistance layer 6 will be described later. Although the thickness of the high resistance layer 6 is not specifically limited, Preferably it is 1-1000 micrometers. Although the size of each semiconductor element 4 is not particularly limited, for example, the height of the quadrangular column is 1 to 50 mm, and the vertical or horizontal width of the bottom surface is about 1 to 50 mm.

  In this embodiment, the internal conductor layer 8 is formed between the high resistance layer 6 and the high resistance layer 6 that are integrally formed at the junction of the semiconductor elements 4 adjacent to each other. At both ends in the Z-axis direction of the internal conductor layer 8, a first terminal portion 8a and a second terminal portion 8b that are electrically connected to the first end portion 4a and the second end portion 4b of the adjacent semiconductor element 4, respectively. Are integrally formed. The first terminal portion 8a is connected to the first end portion 4a of the element 4, and the second terminal portion 8b is connected to the second end portion 4b of the element 4 different from the element 4 to which the first terminal portion 8a is connected. Is done.

  In the embodiment shown in FIG. 1, three semiconductor elements 4 are linearly arranged in the X-axis direction belonging to a plane perpendicular to the Z-axis, but the number of arrangement is not particularly limited. When the semiconductor elements 4 are linearly arranged in the X-axis direction, extraction electrodes 10 and 12 are formed on the semiconductor elements 4 located at both ends in the X-axis direction.

  One extraction electrode 10 is connected to the first end portion 4a of the semiconductor element 4 in order to pair with the second terminal portion 8b of the internal conductor layer 8 connected to the second end portion 4b of the semiconductor element 4. The first terminal portion 10a is integrally formed. The extraction electrode 10 extends on the outer surface of the high resistance layer 6 formed on the side surface of the semiconductor element 4 to the vicinity of the second end 4b in the Z-axis direction.

  The other extraction electrode 12 is connected to the second end portion 4b of the semiconductor element 4 in order to form a pair with the first terminal portion 8a of the inner conductor layer 8 connected to the first end portion 4a of the semiconductor element 4. It is formed in such a pattern. Wiring is connected to these extraction electrodes 10 and 12, and the wiring is connected to each extraction electrode 10 and 12 on the second end portion 4 b side of the semiconductor element 4 as far as possible from the heat source. It is preferable. This is to prevent the durability of the wiring from being lowered by heat from the heat source.

  In this embodiment, the width of the inner conductor layer 8 in the Y-axis direction (the direction perpendicular to the X-axis and the Z-axis and perpendicular to the paper surface) is narrower than the width of the high-resistance layer 6 in the Y-axis direction. The material of the inner conductor layer 8 may be the same as or different from that of the extraction electrodes 10 and 12. The thickness of the inner conductor layer 8 may be the same as or different from that of the extraction electrodes 10 and 12, but is preferably 1 μm to 500 μm, more preferably 3 μm to 500 μm, and particularly preferably 5 μm to 300 μm. It is.

  The semiconductor element 4 is a semiconductor element having the same conductivity type thermoelectric effect (for example, Seebeck effect), which is all n-type or p-type. For example, the semiconductor element 4 is comprised with the composition for n type thermoelectric elements shown below.

Specifically, the composition for an n-type thermoelectric element of the present embodiment contains Ca: 40 to 60 mol% and Mn: 40 to 60 mol% as main components in a metal element ratio. The content ratio of Ca and Mn in the main component is preferably about the same. The composition for an n-type thermoelectric element contains at least one of Zn, Ba, Mg, Sr, and Sn as an additive component with respect to CaMnO _{3 in} which the total amount of Ca and Mn is 100 mol%. Yes. The additive component is mixed with the main component as ZnO, BaCO ₃ , MgO, SrCO ₃ , SnO ₂ or the like in the raw material state.

The additive component is added to CaMnO ₃ containing Ca and Mn in the above ratios in an amount of 0.1 to 50 mol% in terms of elements with respect to 100 mol% of Ca and Mn in total. By containing an additive component in such a range, the absolute value of the Seebeck coefficient α100 at 100 ° C. becomes larger than that of pure CaMnO ₃ . Guess As one of the reasons, Mixing the additive CaMnO _3, and the ₃ crystal CaMnO, formed hetero-phase by the addition component, the heterophasic is to provide some effect against the Seebeck coefficient α Is done. Detailed experimental data is described in Japanese Patent Application No. 2006-268394.

  The Seebeck coefficient α is an electromotive force generated per unit temperature difference (1 ° C.). The n-type thermoelectric semiconductor element has a negative Seebeck coefficient. The Seebeck coefficient α is a factor that greatly affects the thermoelectric conversion characteristics (performance) of the n-type thermoelectric semiconductor element. Specifically, the thermoelectric conversion performance increases in proportion to the square of the Seebeck coefficient α. Therefore, in an n-type thermoelectric semiconductor element having a negative Seebeck coefficient, efficient thermoelectric conversion (power generation) can be performed as the Seebeck coefficient α decreases, that is, as the absolute value of the Seebeck coefficient α increases.

  The thermoelectric conversion performance is also affected by the specific resistance ρ of the n-type thermoelectric element, and increases in proportion to the inverse of the specific resistance ρ. That is, the smaller the specific resistance ρ of the n-type thermoelectric element, the better the thermoelectric conversion performance.

When Zn or Mg is added to CaMnO ₃ , the absolute value of the Seebeck coefficient α of the n-type thermoelectric semiconductor element is increased and the specific resistance ρ of the n-type thermoelectric semiconductor element is kept low. Therefore, sufficiently efficient thermoelectric conversion can be performed by using a composition obtained by adding Zn or Mg to CaMnO ₃ as the material of the n-type thermoelectric element. Further, ZnO has the advantages that it is harmless, is relatively inexpensive, is easy to handle, and a fine raw material can be obtained. Therefore, in consideration of their advantages in addition to thermoelectric conversion characteristics, it is most preferable to use ZnO as an additive. The added amount of Zn is most preferably 10 mol%.

When Sn, Ba, Sr is added to CaMnO ₃ , the absolute value of the Seebeck coefficient α of the n-type thermoelectric element increases, but the specific resistance ρ of the n-type thermoelectric element increases to some extent. However, the Seebeck coefficient α has a larger influence on the thermoelectric conversion characteristics of the n-type thermoelectric element than the specific resistance ρ of the n-type thermoelectric element. Therefore, even when Sn, Ba, Sr is added to CaMnO ₃ , it is possible to ensure good thermoelectric conversion characteristics.

  In this embodiment, the high resistance layer 6 shown in FIG. 1 is composed of a ceramic layer containing, as main components, Ca: 32 to 37 mol% and Mn: 63 to 68 mol% in a metal element ratio, and an additive component such as Zn. Is not included, but additives such as Zr, Fe, Ni, and Al may be included.

  In the present embodiment, the internal conductor layer 8 is a mixed layer (composite layer) of a first component made of a metal component and a second component made of a component constituting the high resistance layer 6. The volume ratio of the second component to the first component is preferably 25:75 to 99: 1, more preferably 30:70 to 90:10, and particularly preferably 35:65 to 70:30.

  Alternatively, the internal conductor layer 8 may be a mixed layer (composite layer) of a first component made of a metal component and a third component made of a component constituting the semiconductor element 4. The volume ratio of the third component to the first component is preferably 25:75 to 99: 1, more preferably 30:70 to 90:10.

  Alternatively, the inner conductor layer 8 may be a mixed layer (composite layer) of the first component, the second component, and the third component. The volume ratio of the second component to the third component with respect to the first component is preferably 25:75 to 99: 1, and more preferably 30:70 to 90:10.

  In the present embodiment, the first component is not particularly limited, and any one of Pt, Au, Ag, Pd, or an alloy thereof is exemplified.

  In order to manufacture the thermoelectric module 2 having the structure shown in FIG. 1, for example, the printing method shown in FIG. 2 or the sheet method shown in FIG. 3 is used. In the printing method, as shown in FIGS. 2 (A) to 2 (C), an electrode paste layer 10a ′ serving as the first terminal portions 10a and 8a shown in FIG. 1 is formed on a support sheet 14 such as a PET film. 8a ′ is formed in a predetermined pattern by screen printing or the like. Thereafter, a resistor paste layer 6 ′ that becomes the high resistance layer 6 shown in FIG. 1, an electrode paste layer 8 ′ that becomes the internal conductor layer 8, and an element paste layer 4 ′ that becomes the semiconductor element 4 are formed in a predetermined pattern by screen printing or the like. Form with.

  The printing is repeated, and finally, the second terminal portion 8b and the electrode paste layers 8b 'and 12' to be the extraction electrode 12 shown in FIG. 1 are formed in a predetermined pattern by screen printing or the like. The intermediate portion of the paste layer laminated portion may be formed by laminating a plurality of paste layer laminated blocks formed separately.

  After the laminate of the paste layer is completed, a binder removal process for removing the organic components contained in the paste layer is performed, and then a baking process is performed. Although the heating temperature at the time of a binder removal process is not specifically limited, It is 250-500 degreeC. Moreover, the heating temperature at the time of baking is preferably 1100 to 1350 ° C. in the air.

  In the sheet method shown in FIGS. 3A to 3F, a semiconductor element green sheet to be the semiconductor element 4 shown in FIG. 1 is formed on a support sheet (not shown) by the doctor blade method or the like. Then, a plurality of these are laminated and pressed so as to have a predetermined thickness to form a laminate 4 ″. Similarly, a resistor green sheet 6 ″ to be the high resistance layer 6 shown in FIG. As shown in FIGS. 3B and 3C, resistor green sheets 6 ″ are laminated and pressed on both surfaces of the semiconductor element green sheet laminate 4 ″.

  Further, as shown in FIG. 3 (D), electrode paste layers 8 ′ and 10 ′ to be the internal conductor layer 8 or the extraction electrode 10 are formed on the surface of the resistor green sheet 6 ″ by the coating method, respectively. Similarly, the electrode paste layer 8 ′ to be the internal conductor layer 8 is formed only on the surface of one of the resistor green sheets 6 ″ by a coating method to obtain a multilayer unit 9a.

  Next, as shown in FIG. 3 (E), the required number of stacked units 9 are stacked, the stacked units 9a are stacked on top, and pressed at a predetermined pressure. After the laminated body after pressing is cut into a predetermined size, as shown in FIG. 3 (F), electrodes to be terminal portions 8a and 8b and take-out electrodes 10 and 12 are formed on both side ends of the pre-firing module 2 ′. Paste layers 8a ′, 8b ′, 10 ′ and 12 ′ are formed. Thereafter, the module 2 'before firing is subjected to binder removal processing and firing processing in the same manner as the printing method.

  In the thermoelectric module 2 according to this embodiment, a plurality of semiconductor elements 4 having the same n-type conductivity type and having a thermoelectric effect are used, and the semiconductor elements 4 that generate a potential difference due to a temperature difference with respect to the heat source are connected in series by the internal conductor layer 8 Has been modularized. Since the elements 4 are connected in series, a relatively high voltage is generated from the extraction electrodes 10 and 12. Moreover, in the present embodiment, the main component of the semiconductor element 4 having the same conductivity type and the main component of the high resistance layer 6 are common. As a result, manufacturing for module integration is facilitated, and there is less risk of cracking or peeling during simultaneous firing. Therefore, the quality of the thermoelectric module 2 is improved and the reliability is improved.

  In the present embodiment, the internal conductor layer 8 is narrower in the Y-axis direction than the high-resistance layer 6 in the Y-axis direction. In addition, the conductor layer 8 is protected by the high resistance layer 6 and is not easily oxidized, thereby improving the reliability.

  Further, in the thermoelectric module 2 according to the present embodiment, the inner conductor layer 8 located inside the high resistance layer 6 includes the first component made of metal and the second component made of a component constituting the high resistance layer 6, or A third component composed of the components constituting the semiconductor element 4 is included. For this reason, even at the time of simultaneous firing, the bonding at the interface between the conductor layer 8 and the high resistance layer 6 is improved, and the bonding between the conductor layer 8 and the semiconductor element 4 is also improved. Etc. can be reduced.

  Furthermore, in the thermoelectric module 2 according to the present embodiment, since the internal conductor layer 8 located inside the high resistance layer 6 includes the second component or the third component together with the first component, this internal conductor. The thermal insulation of the layer 8 is improved as compared with a conductor layer made of only metal. In the thermoelectric module 2 according to the present embodiment, the inner conductor layer 8 extends from the high temperature side to the low temperature side with respect to the heat source. Therefore, the thermal insulation is improved, so that the thermoelectric efficiency is improved.

  As a modification of the thermoelectric module 2 shown in FIG. 1, the thermoelectric module 2 is configured to be covered with the high resistance layer 6 so that only part of the extraction electrodes 10 and 12 are exposed to the outside. good. A method for manufacturing such a thermoelectric module is shown in FIG.

  As shown in FIG. 4A, first, a resistor paste layer 6 'to be a high resistance layer 6 covering the outer periphery is formed by a screen printing method or the like. The resistor paste layer 6 'may be a laminate of resistor green sheets formed by a doctor blade method. The process shown in FIGS. 4B and 4C is the same as the process shown in FIG. 2B except that the resistor paste layer 6 ′ is also formed outside the electrode paste layer 10 ′. .

Finally, as shown in FIG. 4D, the resistor paste layer 6 ′ is formed so that the electrode paste layer 12 ′ to be the extraction electrode 12 is exposed. The subsequent steps are the same as those in the embodiment shown in FIG.
Second embodiment

  The thermoelectric module 2a according to the embodiment shown in FIG. 5 has the same configuration as the thermoelectric module 2 according to FIG. 1 except for the following, has the same operational effects, and redundant description is omitted. To do.

  As shown in FIG. 5, the thermoelectric module 2 a according to the present embodiment covers the entire circumference of each of the square columnar semiconductor elements 4 with the high resistance layer 6, and the high resistance layer 6 located at the junction of the adjacent elements 4. An internal conductor layer 80 is embedded inside. The inner conductor layer 80 corresponds to the inner conductor layer 8 shown in FIG.

  The internal conductor layer 80 is integrally formed with a first terminal portion 80a and a second terminal portion 80b that are respectively connected to the first end 4a and the second end 4b of the adjacent semiconductor elements. The first terminal portion 80a and the second terminal portion 80b are connected to the element 4 at different side surface positions of the element 4 in the Z-axis direction. For example, the first terminal portion 80a is connected to the side surface of the first end portion 4a of the element 4, and the second terminal portion 80b is a second end portion of the element 4 different from the element 4 to which the first terminal portion 80a is connected. It is connected to the side surface of 4b.

  On one of the semiconductor elements 4 located at both ends in the X-axis direction, the extraction electrode 100 similar to the internal conductor layer 80 is formed inside the high resistance layer 6 located outside the semiconductor element 4. The extraction electrode 100 includes a first terminal portion 100 a connected to the first end portion 4 a of the element 4 and a second terminal portion 100 b formed on the second end portion 4 b side and exposed to the outside of the high resistance layer 6. Have. A wiring is connected to the second terminal portion 100b.

  In order to form a pair with the first terminal portion 80a of the internal conductor layer 80 connected to the first end portion 4a of the semiconductor element 4 on the other side of the semiconductor element 4 located at both ends in the X-axis direction, the semiconductor element 4 The extraction electrode 120 is formed in such a pattern as to be connected to the second end 4b.

  The thermoelectric module 2a shown in FIG. 5 is manufactured, for example, as shown in FIGS. 6 (A) to 6 (F). That is, first, as shown in FIG. 6A, a semiconductor element green sheet to be the semiconductor element 4 shown in FIG. 5 is formed on a support sheet (not shown) by a doctor blade method or the like, A plurality of stacked layers are pressed so as to have a thickness, and a stacked body 4 ″ is formed.

  Similarly, a resistor green sheet 6 ″ to be the high resistance layer 6 shown in FIG. 5 is formed by a doctor blade method or the like. Each resistor green sheet 6 ″ is formed with a through hole 7 by laser or punching. Is formed in a necessary place. Thereafter, as shown in FIGS. 6B and 6C, resistor green sheets 6 ″ are laminated and pressed on both surfaces of the semiconductor element green sheet laminate 4 ″.

  Further, as shown in FIG. 6D, an electrode paste layer 80 ′, which becomes the internal conductor layer 80, is formed on the surface of the resistor green sheet 6 ″ by the printing method to obtain the multilayer unit 11. 80 ′ enters the through hole 7 and is connected to the stacked body 4 ″ of the semiconductor element green sheet.

  Similarly, an electrode paste layer 80 ′ to be an internal conductor layer 80 is formed only on the surface of one resistor green sheet 6 ″ by a printing method, and a through hole is formed in the other resistor green sheet 6 ″. A laminated unit 11a that is not formed is obtained.

  Next, as shown in FIG. 6 (E), the required number of stacked units 11 are stacked, the stacked units 11a are stacked at the bottom, and pressed at a predetermined pressure. The pressed laminate is cut into a predetermined size to obtain a pre-firing module 2a 'as shown in FIG. 6 (F). A resistor paste layer 6 ′ to be the high resistance layer 6 is formed on both side ends of the pre-fired module 2 a ′ by a coating method to form electrode paste layers to be the extraction electrodes 100 and 120 shown in FIG. 5. Thereafter, the binder removal process and the baking process are performed on the pre-fired module 2a 'in the same manner as in the above-described embodiment.

  7 and 8 show a manufacturing method according to still another embodiment. First, as shown in FIG. 7A, a semiconductor element green sheet to be the semiconductor element 4 shown in FIG. 5 is formed by a doctor blade method or the like on a support sheet that is not shown in the figure. A plurality of sheets are stacked and pressed to form a stacked body 4 ″.

  Next, as shown in FIG. 7B, a resistor paste layer 6 ′ to be the high resistance layer 6 shown in FIG. 5 is formed on the surface of the semiconductor element green sheet laminate 4 ″ by screen printing or the like. In the resistor paste layer 6 ′, through holes 7 are formed in necessary places in a predetermined pattern.

  Thereafter, as shown in FIG. 7C, an electrode paste layer 80 'to be the internal conductor layer 80 is formed on the surface of the resistor paste layer 6' by a printing method. The electrode paste layer 80 ′ enters the through hole 7 and is connected to the stacked body 4 ″ of semiconductor element green sheets.

  Next, as shown in FIGS. 7D and 7E, a pair of primary laminated units 13 shown in FIG. 7C is prepared, and one primary laminated unit 13 is inverted, and a semiconductor element green sheet The secondary laminate unit 15 is obtained by press-molding so that the laminates 4 ″ are in contact with each other.

  Similarly, an electrode paste layer 80 ′ to be the internal conductor layer 80 is formed only on the surface of one resistor paste layer 6 ′ by a printing method, and a through hole is formed in the other resistor paste layer 6 ′. A laminated unit 15a that is not formed is obtained.

Next, as shown in FIG. 7 (F) and FIG. 8 (A), the required number of stacked units 15 are stacked, the stacked units 15a are stacked at the bottom, and pressed at a predetermined pressure. The laminated body after pressing is cut into a predetermined size to obtain a pre-firing module 2a ″ as shown in FIG. 8B. The high resistance layer 6 and the two-side end portions of the pre-firing module 2a ″ are obtained. The resistor paste layer 6 ′ to be formed is formed by a coating method to form an electrode paste layer to be the extraction electrodes 100 and 120 shown in FIG. After that, if the binder removal process and the baking process are performed on the pre-firing module 2a ″ in the same manner as the above-described embodiment, the thermoelectric module 2a shown in FIG. 5 is obtained.
Third embodiment

  The thermoelectric module 2b according to the embodiment shown in FIG. 9 has the same configuration as the thermoelectric module 2 according to FIG. 1 except for the following, has the same effects, and redundant description is omitted. To do.

As shown in FIG. 9, in the thermoelectric module 2b of this embodiment, the semiconductor elements 4 according to FIG. 1 are arranged in a matrix in the X-axis direction and the Y-axis direction, and form a flat plate block as a whole. . And in order to connect all these elements 4 in series with the heat source located in the 1st edge part 4a side, the arrangement position of the internal conductor layer 8 is devised. That is, the element 4 in which the inner conductor layer 8 is disposed on the two opposite side surfaces of the element 4 and the element 4 in which the inner conductor layer 8 is disposed on the two adjacent side surfaces of the element 4 are combined.
Fourth embodiment

  The thermoelectric module 2c according to the embodiment shown in FIG. 10 has the same configuration as the thermoelectric module 2 according to FIG. 1 except for the following, has the same operational effects, and redundant description is omitted. To do.

  As shown in FIG. 10, in the thermoelectric module 2 c of this embodiment, the semiconductor element 40 corresponding to the semiconductor element 4 according to FIG. 1 is formed in the shape of a ring divided piece, and the inner peripheral side and the outer peripheral side of the ring divided piece 40 are A first end 40a and a second end 40b are formed, and these semiconductor elements 40 are combined to form a cylindrical ring.

  A heat source is disposed at the center of the cylindrical ring. The heat source located at the center of the cylindrical ring may be, for example, a chimney or a pipe. In this embodiment, the first ends connected to the first end portion 40a and the second end portion 40b of the adjacent semiconductor element 40 are respectively connected to both ends of the inner conductor layer 280 corresponding to the inner conductor layer 80 shown in FIG. A terminal portion 280a and a second terminal portion 280b are formed.

  In the embodiment shown in FIG. 10, the extraction electrode 220 having the same structure as the internal conductor layer 280 corresponds to the extraction electrode 12 shown in FIG. 1, and the extraction electrode 200 corresponds to the extraction electrode 10 shown in FIG.

  The thermoelectric module 2c shown in FIG. 10 may be integrally formed in a ring shape, but as shown in FIG. 11 or FIG. 12, a split type thermoelectric module 2d or 2e configured by dividing the ring into a plurality of parts is combined. May be configured. In the example shown in FIG. 11, after the split thermoelectric module 2d is combined, it becomes the same as the thermoelectric module 2c shown in FIG. 10. However, in the example shown in FIG. .

  In the thermoelectric module 2e shown in FIG. 12, extraction electrodes 300 and 320 are respectively formed in the high resistance layer 6 of the semiconductor element 40 located at the circumferential end of the ring. These extraction electrodes 300 and 320 correspond to the extraction electrodes 10 and 12 shown in FIG.

  The present invention is not limited to the above-described embodiment, and can be variously modified within the scope of the present invention.

  For example, in the above-described embodiment, an n-type semiconductor element is used as the semiconductor elements 4 and 40 having the thermoelectric effect. However, as long as the semiconductor element has a thermoelectric effect that can be baked in an oxidizing atmosphere such as in the air, There is no particular limitation. For example, as the semiconductor elements 4 and 40, a p-type semiconductor element containing Mn and Co as main components and containing Cu as an additive component can also be used.

Hereinafter, the present invention will be described based on further detailed examples.
Example 1

Commercially available manganese tetroxide and calcium carbonate are prepared as raw materials for the composition for an n-type thermoelectric element, and these are weighed and blended so that the molar ratio of Mn to Ca is 50 mol to 50 mol. Furthermore, Ca and Mn ZnO was weighed and blended as an additional component at a ratio of 10 moles with respect to CaMnO ₃ with a total of 100 moles. These were wet mixed in a ball mill for 16 hours, and the resulting raw material mixture was dehydrated and dried, and then powdered using a mortar and pestle. Next, the powder was calcined at 800 to 1200 ° C. for 2 hours.

  Next, this temporarily fired body was pulverized by a ball mill, dehydrated and dried. An organic binder, an organic solvent, a plasticizer and the like were added to the finely pulverized powder (third component powder), and the mixture was pulverized for about 20 hours using a ball mill or the like to prepare an element paste. The element paste is a paste for forming the semiconductor element 4 shown in FIG.

  Moreover, the resistor paste used as the high resistance layer 6 shown in FIG. 1 was produced as follows. That is, commercially available manganese tetroxide and calcium carbonate were prepared, these were weighed and blended so that the molar ratio of Mn and Ca was 66 moles to 34 moles, and these were wet mixed in a ball mill for 16 hours. The mixture was dehydrated and dried and then powdered using a mortar and pestle. Next, the powder was calcined at 800 to 1200 ° C. for 2 hours.

  Next, this temporarily fired body was pulverized by a ball mill, dehydrated and dried. An organic binder, an organic solvent, a plasticizer, and the like were added to the finely pulverized powder (second component powder), and the mixture was pulverized and mixed for about 20 hours using a ball mill or the like to prepare a resistor paste.

  Furthermore, an electrode paste to be the internal electrode layer 8 shown in FIG. 1 was produced as follows. Pd powder having an average particle diameter of 0.8 μm and the second component powder having an average particle diameter of 2.0 μm are mixed at a volume ratio of 50:50, and an organic binder and an organic solvent are mixed therein. An electrode paste was prepared.

  Using these element pastes, resistor pastes, and electrode pastes, electrode paste layers 10a ′ and 8a ′ are formed on a support sheet 14 such as a PET film as shown in FIGS. The resistor paste layer 6 ′, the electrode paste layer 8 ′, and the element paste layer 4 ′ were formed in a predetermined pattern by screen printing or the like. The thickness of the electrode paste layers 10a ′ and 8a ′ in the Z-axis direction was 50 μm. The width of the element paste layer 4 ′ in the X-axis direction was 2000 μm, the width of the resistor paste layer 6 ′ in the X-axis direction was 100 μm, and the width of the electrode paste layer 8 ′ in the X-axis direction was 50 μm.

  The printing is repeated until the height in the Z-axis direction becomes 3 mm. Finally, the second terminal portion 8b and the electrode paste layers 8b ′ and 12 ′ to be the extraction electrode 12 shown in FIG. A predetermined pattern was formed by printing or the like. The drying of the printing paste was 150 ° C. for 30 minutes.

The resulting laminate was pressed for 1 minute in a stacking press at a pressure of 49 MPa (500 kg / cm ² ) in the stacking direction, and then subjected to binder removal processing and firing processing. The heating temperature and heating time during the binder removal treatment were 250 to 500 ° C. and 2 hours, respectively. Moreover, the heating temperature and heating time at the time of baking were 1100-1350 degreeC and 2 hours in air | atmosphere.

  The element cross section of the obtained thermoelectric module 2 is polished, and the interface between the semiconductor element 4 and the high resistance layer 6, the interface between the high resistance layer 6 and the internal conductor layer 8, the terminal portions 8 a and 8 b and the semiconductor element with an electron microscope The presence or absence of cracks was examined at the interface with 4, but no cracks were observed in 10 samples.

Further, from the observation result of the electron micrograph, in the conductor layer 6, the second component which is the high resistance layer is included in the matrix of the first component in which the first component composed of the metal component is three-dimensionally connected. Was confirmed to be dispersed. Furthermore, it has been confirmed that the electrical resistance of the conductor layer 6 is almost the same as that of a conductor layer made of only a metal component. Furthermore, the thermal conductivity indicating the thermal insulation of the conductor layer 6 is reduced to about ¼ or less compared to a conductor layer made of only a metal component, so that the thermal insulation is improved and the thermoelectric efficiency is expected to be improved. I was able to confirm that it was possible.
Example 2

  A thermoelectric module 2 was produced in the same manner as in Example 1 except for the following. In this example, the sheet method shown in FIG. 3 was used. That is, a semiconductor element green sheet (80 mm × 80 mm) to be the semiconductor element 4 shown in FIG. 1 is formed on a support sheet (not shown) by the doctor blade method, and a plurality of these are formed to be 1.2 mm. The sheets were laminated and pressed to form a laminate 4 ″ shown in FIG.

  Similarly, the resistor green sheet 6 ″ to be the high resistance layer 6 shown in FIG. 1 is formed by the doctor blade method, and as shown in FIGS. 3B and 3C, the semiconductor element green sheet is formed. A resistor green sheet 6 ″ was laminated and pressed on both sides of the laminate 4 ″. The thickness of the resistor green sheet 6 ″ was 30 μm.

  Further, as shown in FIG. 3D, electrode paste layers 8 ′ and 10 ′ to be the internal conductor layer 8 or the extraction electrode 10 are formed on the surface of the resistor green sheet 6 ″ by the coating method, respectively, and the temperature is 150 °. The laminated unit 9 was obtained by drying at C and 30 minutes. Similarly, an electrode paste layer 8 ′ to be the internal conductor layer 8 was formed only on the surface of one of the resistor green sheets 6 ″ by a coating method. As a result, a laminated unit 9a was obtained.

Next, as shown in FIG. 3 (E), the required number of stacked units 9 are stacked, the stacked units 9a are stacked on the top, and the resulting stacked body is 49 MPa (500 kg) in the stacking direction with a stacking press. / cm ² ) for 1 minute. Thereafter, the laminate is cut into a size of 10 mm × 6 mm, and as shown in FIG. 3 (F), terminal portions 8a and 8b and extraction electrodes 10 and 12 are formed at both side ends of the pre-firing module 2 ′. Electrode paste layers 8a ′, 8b ′, 10 ′, and 12 ′ were formed. Thereafter, the module 2 ′ before firing was subjected to binder removal processing and firing processing in the same manner as in Example 1.

Although the same evaluation as Example 1 was performed about the obtained thermoelectric module 2, the same result was obtained.
Example 3

  A thermoelectric module 2 was produced in the same manner as in Example 1 except for the following. In this example, the printing method shown in FIG. 4 was used. That is, as shown in FIG. 4A, first, a resistor paste layer 6 ', which becomes the high resistance layer 6 covering the outer periphery, was formed by screen printing with a thickness of 100 μm. The steps shown in FIGS. 4B and 4C were performed in the same manner as in Example 1 except that the resistor paste layer 6 ′ was also formed outside the electrode paste layer 10 ′.

  Finally, as shown in FIG. 4D, the resistor paste layer 6 'was formed so that the electrode paste layer 12' serving as the extraction electrode 12 was exposed. Subsequent steps were performed in the same manner as in Example 1.

Although the same evaluation as Example 1 was performed about the obtained thermoelectric module 2, the same result was obtained.
Example 4

  A thermoelectric module 2a shown in FIG. 5 was produced in the same manner as in Example 1 except for the following. In this example, as shown in FIG. 6, the thermoelectric module 2a was produced by using a sheet method and a printing method.

  That is, first, as shown in FIG. 6 (A), a semiconductor element green sheet to be the semiconductor element 4 shown in FIG. 5 is formed on a support sheet (not shown) by the doctor blade method, and these are formed to a predetermined thickness. A plurality of laminates 4 ″ were pressed to form a laminate 4 ″ having a thickness of 1.2 mm.

  Similarly, a resistor green sheet 6 ″ to be the high resistance layer 6 shown in FIG. 5 was formed with a thickness of 30 μm by a doctor blade method or the like. Each resistor green sheet 6 ″ was through-holed with a laser. 7 was formed in a necessary place. The inner diameter of the through hole 7 was 50 μm. Thereafter, as shown in FIGS. 6B and 6C, resistor green sheets 6 ″ were laminated and pressed on both sides of the semiconductor element green sheet laminate 4 ″.

  Further, as shown in FIG. 6 (D), electrode paste layers 80 ′, which respectively become internal conductor layers 80, are formed on the surface of the resistor green sheet 6 ″ by a printing method to a thickness of 15 μm. And dried to obtain a laminated unit 11. The electrode paste layer 80 ′ entered the through hole 7 and was connected to the laminated body 4 ″ of the semiconductor element green sheet.

  Similarly, an electrode paste layer 80 ′ to be the internal conductor layer 80 is formed with a thickness of 15 μm by a printing method only on the surface of one resistor green sheet 6 ″, and the other resistor green sheet 6 ″ is formed on the other resistor green sheet 6 ″. Obtained a laminated unit 11a in which no through hole was formed.

  Next, as shown in FIG. 6E, the required number of stacked units 11 were stacked, the stacked units 11a were stacked at the bottom, and pressed at a predetermined pressure. The pressing conditions were the same as in Example 1. Thereafter, as shown in FIG. 6 (F), the laminate was cut into a size of 10 mm × 6 mm to obtain a pre-firing module 2a ′.

  A resistor paste layer 6 ′ to be the high resistance layer 6 was formed on both side ends of the pre-fired module 2 a ′ by a coating method, and electrode paste layers to be the extraction electrodes 100 and 120 shown in FIG. 5 were formed. Thereafter, the binder removal process and the baking process were performed on the pre-fired module 2a 'in the same manner as in Example 1.

Although the same evaluation as Example 1 was performed about the obtained thermoelectric module 2a, the same result was obtained.
Example 5

  A thermoelectric module 2a shown in FIG. 5 was produced in the same manner as in Example 1 except for the following. In this example, as shown in FIGS. 7 and 8, a thermoelectric module 2a was manufactured by using a sheet method and a printing method.

  Specifically, as shown in FIG. 7A, first, a semiconductor element green sheet to be the semiconductor element 4 shown in FIG. 5 is formed on a support sheet (not shown) by the doctor blade method. A plurality of laminates 4 ″ were formed by laminating and pressing so as to have a thickness of 2 mm.

  Next, as shown in FIG. 7B, a resistor paste layer 6 ′ to be the high resistance layer 6 shown in FIG. 5 was formed on the surface of the laminate 4 ″ of the semiconductor element green sheet by screen printing. The thickness of the resistor paste layer 6 ′ was 20 μm, and through holes 7 having an inner diameter of 50 μm were formed in the resistor paste layer 6 ′ where necessary.

  After that, as shown in FIG. 7C, an electrode paste layer 80 ′ to be the internal conductor layer 80 is formed on the surface of the resistor paste layer 6 ′ by a printing method, under the conditions of 150 ° C. and 30 minutes. Dried. The electrode paste layer 80 ′ entered the through hole 7 and connected to the semiconductor element green sheet laminate 4 ″. The thickness of the electrode paste layer 80 ′ was 10 μm.

  Thereafter, as shown in FIG. 7D and FIG. 7E, a pair of primary laminated units 13 shown in FIG. 7C is prepared, and one primary laminated unit 13 is inverted, and a semiconductor element green sheet The laminates 4 ″ were press-molded so that they were in contact with each other to obtain a secondary laminate unit 15.

  Similarly, an electrode paste layer 80 ′ to be the internal conductor layer 80 is formed only on the surface of one resistor paste layer 6 ′ by a printing method, and a through hole is formed in the other resistor paste tank 6 ′. An unformed multilayer unit 15a was obtained.

Next, as shown in FIG. 7 (F) and FIG. 8 (A), the required number of stacked units 15 are stacked, the stacked unit 15a is stacked at the bottom, and a pressure of 49 MPa (500 kg / cm ² ) is applied for 1 minute. After pressurization, the pressed laminate was cut into a size of 10 mm × 6 mm to obtain a pre-firing module 2a ″ as shown in FIG. 8B. Both side ends of this pre-firing module 2a ″ The resistor paste layer 6 ′ to be the high resistance layer 6 was formed by a coating method to form electrode paste layers to be the extraction electrodes 100 and 120 shown in FIG. Thereafter, the pre-firing module 2a ″ was subjected to binder removal processing and firing processing in the same manner as in Example 1 described above to obtain a thermoelectric module 2a shown in FIG.

Although the same evaluation as Example 1 was performed about the obtained thermoelectric module 2a, the same result was obtained.
Example 6

  Instead of using Pd powder, any powder of Pt, Au, Ag, or any alloy powder of Pt, Au, Ag, Pd was used to form an electrode paste to be the internal electrode layer 8 Produced a thermoelectric module 2 in the same manner as in Example 1.

Although the same evaluation as Example 1 was performed about the obtained thermoelectric module 2, the same result was obtained.
Example 7

  A thermoelectric module 2 was produced in the same manner as in Example 1 except that the Pd powder and the second component powder were mixed by changing the volume ratio in the range of 1:99 to 99: 1.

Although the same evaluation as Example 1 was performed about the obtained thermoelectric module 2, the same result was obtained.
Example 8

  A thermoelectric module 2 was produced in the same manner as in Example 1 except that the Pd powder and the third component powder were mixed by changing the volume ratio in the range of 1:99 to 99: 1.

  Although the same evaluation as Example 1 was performed about the obtained thermoelectric module 2, the same result was obtained.

FIG. 1 is a schematic cross-sectional view of a thermoelectric module according to an embodiment of the present invention. 2 (A) to 2 (C) are cross-sectional views of relevant parts showing an example of the manufacturing process of the thermoelectric module shown in FIG. FIGS. 3A to 3C are cross-sectional views of relevant parts showing another example of the manufacturing process of the thermoelectric module shown in FIG. 4 (A) to 4 (D) are cross-sectional views illustrating the main part of another example of the manufacturing process according to a modification of the thermoelectric module shown in FIG. FIG. 5 is a schematic cross-sectional view of a thermoelectric module according to another embodiment of the present invention. 6 (A) to 6 (F) are cross-sectional views of relevant parts showing an example of the manufacturing process of the thermoelectric module shown in FIG. 7 (A) to 7 (F) are cross-sectional views of relevant parts showing another example of the manufacturing process of the thermoelectric module shown in FIG. FIGS. 8A and 8B are cross-sectional views of relevant parts showing another example of the manufacturing process of the thermoelectric module shown in FIG. FIG. 9 is a schematic perspective view of a thermoelectric module according to still another embodiment of the present invention. FIG. 10 is a schematic cross-sectional view of a thermoelectric module according to still another embodiment of the present invention. FIG. 11 is a schematic cross-sectional view of a thermoelectric module according to still another embodiment of the present invention. FIG. 12 is a schematic cross-sectional view of a thermoelectric module according to still another embodiment of the present invention.

Explanation of symbols

2, 2a to 2e ... thermoelectric module 4, 40 ... semiconductor element 4a ... first end 4b ... second end 6 ... high resistance layer 8, 80, 280 ... internal conductor layer 8a, 80a, 280a ... first terminal part 8b, 80b, 280b ... 2nd terminal part 10, 12, 100, 120, 200, 220, 300, 320 ... Extraction electrode

Claims (13)

A plurality of semiconductor elements of the same conductivity type and having a thermoelectric effect;
A high resistance layer integrally formed at the junction of adjacent semiconductor elements;
A thermoelectric module having a conductor layer integrally formed inside the high-resistance layer and electrically connecting the first end and the second end of adjacent semiconductor elements,
The thermoelectric module in which the conductor layer is a mixed layer of a first component made of metal and a second component made of a component constituting the high resistance layer. A plurality of semiconductor elements of the same conductivity type and having a thermoelectric effect;
A high resistance layer integrally formed at the junction of adjacent semiconductor elements;
A thermoelectric module having a conductor layer integrally formed inside the high-resistance layer and electrically connecting the first end and the second end of adjacent semiconductor elements,
The thermoelectric module, wherein the conductor layer is a mixed layer of a first component made of metal and a third component made of a component constituting the semiconductor element.   2. The thermoelectric module according to claim 1, wherein in the conductor layer, the second component is dispersed in a matrix of the first component in which the first component is connected in a three-dimensional manner.   3. The thermoelectric module according to claim 2, wherein in the conductor layer, the third component is dispersed in a matrix of the first component in which the first component is connected in a three-dimensional manner.   The thermoelectric module according to claim 1, wherein a main component of the semiconductor element and a main component of the high resistance layer are common.   The thermoelectric module according to claim 5, wherein both the main component of the semiconductor element and the main component of the high resistance layer contain Mn and Ca. The width of the conductor layer is narrower than the width of the high resistance layer,
The thermoelectric module according to claim 1, wherein a width of the high resistance layer is equal to or less than a width of the semiconductor element.   The first terminal portion and the second terminal portion connected respectively to the first end portion and the second end portion of adjacent semiconductor elements are formed at both ends of the conductor layer. The thermoelectric module described in 1.   The thermoelectric module according to claim 8, wherein the high resistance layer covers a periphery other than an end face of the semiconductor element to which the first terminal portion and the second terminal portion are connected.   The thermoelectric module according to claim 8, wherein the high resistance layer covers the entire periphery other than the connection portion of the semiconductor element to which the first terminal portion and the second terminal portion are connected.   Each semiconductor element has a quadrangular prism shape, both ends of the quadrangular prism are the first end and the second end, and the semiconductor elements are arranged in a matrix. A thermoelectric module according to any one of the above.   Each semiconductor element has a shape of a ring split piece, and the inner peripheral side and the outer peripheral side of the ring split piece are the first end and the second end, and these semiconductor elements form at least a part of the ring. The thermoelectric module according to claim 1, wherein the thermoelectric module is arranged as described above.   The thermoelectric module according to any one of claims 1 to 12, wherein the semiconductor element, the high-resistance layer, and the conductor layer are formed by sheet molding or printing, and are integrated by simultaneous firing.

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