JP4385898B2 - Method for manufacturing thermoelectric conversion element - Google Patents

Description

The present invention relates to a method for manufacturing a thermoelectric conversion element.

  Conventionally, raw material powder is put into a sintering jig in a chamber, sandwiched between an upper punch and a lower punch, and a predetermined pressurizing force is applied from both to the upper and lower punch electrodes respectively connected to the upper and lower punch electrodes. There is a method for manufacturing a thermoelectric conversion element in which a pulse current is supplied from a sintering power source and plasma is discharged between powder particles to sinter (see Patent Document 1).

And in the manufacturing method of such a thermoelectric conversion element, the method of cut | disconnecting a sintered material into a chip-shaped element by a grid pattern with a dicing blade is used.
Japanese Patent Laid-Open No. 5-55640

  However, when the sintered material is cut into chip-like elements in a grid pattern with a dicing blade, an element having a cutting allowance (corresponding to the thickness of the dicing blade) is wasted. That is, for example, if the chip-shaped element is 0.65 mm square, if the chip-shaped element is cut with a dimming blade having a thickness of 0.2 mm, the periphery of the chip-shaped element is cut by 0.2 mm. In order to cut the element, a size of 0.85 mm square is required in consideration of the adjacent chip-shaped element. In addition, large-scale dicing equipment is required.

The present invention has been made to solve the above-described problems, and an object of the present invention is to provide a method for manufacturing a thermoelectric conversion element in which elements are not wasted and no large-scale dicing equipment is required.

In order to solve the above problems, a method for manufacturing a thermoelectric conversion element of the present invention includes a step of manufacturing a sintered material having a predetermined shape for a thermoelectric conversion element, and at least one surface of the surface and the back surface of the sintered material. A step of performing plating for the electrode layer, and a step of pushing the sintered material subjected to the plating for the electrode layer into a partition block divided into the size of the chip-shaped element to separate it into chip-shaped elements. It is what.

The method for manufacturing a thermoelectric conversion element of the present invention includes a step of manufacturing a sintered material having a predetermined shape for a thermoelectric conversion element, and a step of bonding an electrode layer to at least one surface of the surface and the back surface of the sintered material. And a step of pushing the sintered material joined with the electrode layer into a partition block divided into chip-like element sizes and separating them into chip-like elements.

  Before joining the electrode layers, a process of forming irregularities on the facing surface of the sintered material can be included.

  The joining of the electrode layer may include a step of sintering and forming a conductive powder material.

  According to the manufacturing method of the present invention, since the sintered material is pushed into the partition block and separated into chip-like elements, the sintered material is not cut by a dicing blade, but is separated by pushing. Since the cost (corresponding to the thickness of the dicing blade) is not required, the waste of the elements is reduced and the yield is improved. In addition, since a shearing force acts on the shearing surface of the chip-like element in the step of pushing the sintered material, the crystals in the element are easily oriented in the pushing direction, so that the performance of the thermoelectric conversion element is improved.

  Hereinafter, the best mode for carrying out the present invention will be described in detail with reference to the drawings.

  FIG. 1 and FIG. 9A are manufacturing process diagrams of the thermoelectric conversion element of the first embodiment.

  An upper punch 2 that moves up and down is provided at the upper part of the chamber 1, and a fixed lower punch 3 is provided at the lower part of the chamber 1. The chamber 1, the upper punch 2 and the lower punch 3 constitute a hot press. The upper punch 2 may be fixed and the lower punch 3 may be moved up and down, or the upper punch 2 and the lower punch 3 may be moved up and down relatively.

  On the upper surface of the lower punch 3, a separation block 4 is installed so as to be removable. As shown in FIGS. 9A and 9C, the partition block 4 has an inner width W that matches the size of the outer width of the chip-like element (thermoelectric conversion element) 11 (for example, 0.65 mm square). These are divided into a grid pattern by the separator 4a. The partition plate 4a has a thickness t of, for example, 0.2 mm, and the tip thereof is formed on the edge portion 4b serving as a separation blade.

  First, the sintered material 10 for thermoelectric conversion elements is manufactured. Although not specifically illustrated, this step is a step of forming the material powder on the sintered material 10 having a predetermined shape by hot pressing or the like. For example, in the case of hot pressing, the temperature is 300 to 600 ° C. and the pressure is 20 to 50 MPa. For 0.5 to 2 hours. The sintered material 10 may have a wafer shape or other shapes. In addition, this process does not need to be performed at all in the process immediately before the process described below, and can be used in the process described below by transporting the sintered material 10 manufactured in another factory.

  Next, as shown in FIG. 1A, the sintered material 10 is put in the chamber 1 and placed on the partition block 4 installed on the lower punch 3. At this time, since the hot press is set to a temperature of 300 to 600 ° C., for example, the sintered material 10 is softened.

  Next, as shown in FIG. 1B, when the upper punch 2 is moved downward, the softened sintered material 10 is pushed into the partition block 4 with a pressure of 20 to 50 MPa, for example, and sheared by the partition plate 4a. The chip-like elements 11 are separated. For example, if the separation block 4 is divided into 100 vertical and horizontal, it is separated into 10,000 chip-like elements 11.

  Thereafter, the chip-shaped element 11 separated in the partition block 4 is cooled and cured in the chamber 1, and the cured chip-shaped element 11 is taken out from the chamber 1 together with the partition block 4, and FIG. The chip-like element (thermoelectric conversion element) 11 can be manufactured by extruding each chip-like element 11 from the separation block 4 using the extrusion jig 5 corresponding to the number of divisions of the separation block 4 as shown in (d). It becomes like this.

  In the above embodiment, pressing was performed in the order of the upper punch 2 → sintered material 10 → separation block 4 → lower punch 3, but the sintered material 10 was placed on the upper surface of the lower punch 3 and the separation block 4 was placed thereon. Then, pressing can be performed in the order of the upper punch 2 → the separation block 4 → the sintered material 10 → the lower punch 3.

  According to the manufacturing method of the first embodiment, since the sintered material 10 is pushed into the partition block 4 and separated into the chip-like elements 11, the sintered material 10 is not cut by a dicing blade, but by pushing. Since the separation is not necessary, a cutting allowance (corresponding to the thickness of the dicing blade) is not required, so that the waste of the elements is reduced and the yield is improved.

  Further, since a shearing force acts on the shearing surface of the chip-like element 11 in the step of pushing the sintered material 10, the crystals in the element are easily oriented in the pushing direction, so that the performance of the thermoelectric conversion element is improved. .

  FIG. 2 and FIG. 9B are manufacturing process diagrams of the thermoelectric conversion element of the second embodiment. The structure of a hot press is the same as 1st Embodiment, and the process of manufacturing the sintered material 10 for thermoelectric conversion elements is also the same.

  In 2nd Embodiment, the plating 13 for electrode layers is given to the surface and back surface of the sintered material 10 which were manufactured, respectively.

  As the electrode layer plating 13, first, nickel (Ni) plating is preferably performed, and then gold (Au) plating is preferably performed on the nickel (Ni) plating.

  Then, as shown in FIG. 2A, the sintered material 10 with the electrode layer plating 13 is placed in the chamber 1 and placed on the partition block 4 installed on the lower punch 3.

  Then, as shown in FIG. 2B, when the upper punch 2 is moved downward, the softened sintered material 10 with electrode layer plating 13 is pushed into the partition block 4, and the electrode layer plating 13 is formed by the partition plate 4a. Together with this, it is separated into a large number of chip-like elements 11.

  Thereafter, the chip-like element 11 separated in the separation block 4 is cooled and cured in the chamber 1, and the cured chip-like element 11 is taken out of the chamber 1 together with the separation block 4, and FIG. As shown in (d), the chip-shaped element 11 with the electrode layer 13 (thermoelectric conversion element) 11 can be manufactured by extruding each chip-shaped element 11 from the separation block 4 using the extrusion jig 5. It is also possible to apply the electrode layer plating 13 only to at least one of the front and back surfaces of the sintered material 10.

  According to the manufacturing method of the second embodiment, in addition to the effects of the first embodiment, the chip-like element (thermoelectric conversion element) 11 with the electrode layer 13 can be easily manufactured. Can be easily attached. Moreover, the adhesion strength between the electrode layer plating 13 and the chip-like element 11 is improved by the pushing force.

  FIG. 3 is a manufacturing process diagram of the thermoelectric conversion element of the third embodiment. The structure of a hot press is the same as 1st Embodiment, and the process of manufacturing the sintered material 10 for thermoelectric conversion elements is also the same.

  In the third embodiment, as shown in FIG. 3A, the lower electrode layer conductive material 14a, the sintered material 10, and the upper electrode conductive material 14b are placed in the chamber 1, and the lower punch 3 The lower electrode layer conductive material 14a is placed on the partition block 4 placed above, the sintered material 10 is placed thereon, and the upper electrode conductive material 14b is placed thereon.

  3B, when the upper punch 2 is moved downward, the lower electrode layer conductive material 14a, the softened sintered material 10 and the upper electrode conductive material 14b are separated into the partition block 4. Pushed in.

  The lower electrode layer conductive material 14a and the upper electrode conductive material 14b are joined to the softened sintered material 10 by the pushing force, and at the same time, the sintered material 10 is used for the lower electrode layer by the partition plate 4a. It is sheared together with the conductive material 14 a and the upper electrode conductive material 14 b so as to be separated into a large number of chip-like elements 11.

  Thereafter, the chip-like element 11 separated in the separation block 4 is cooled and cured in the chamber 1, and the cured chip-like element 11 is taken out of the chamber 1 together with the separation block 4, and FIG. As shown in (d), the chip-like elements (thermoelectric conversion elements) 11 with the electrode layers 14a and 14b can be manufactured by extruding each chip-like element 11 from the separation block 4 using the extrusion jig 5. Become. It is also possible to bond the electrode layer 14a or 14b only to at least one of the front and back surfaces of the sintered material 10.

  According to the manufacturing method of the third embodiment, in addition to the effects of the first embodiment, the step of joining the electrode layers 14a, 14b and the step of separating into the chip-like elements 11 can be performed at the same time, so the electrode layers 14a, 14b The attached chip-like element (thermoelectric conversion element) 11 can be efficiently manufactured. Further, the adhesion strength between the electrode layers 14a and 14b and the chip-like element 11 is improved by the pushing force.

  FIG. 4 is a manufacturing process diagram of a thermoelectric conversion element according to a modification of the third embodiment.

  In the modification of the third embodiment, as shown in FIG. 4A, the lower electrode layer conductive material 14a, the partition block 4, the sintered material 10, and the upper electrode conductive material 14b are placed in the chamber 1. The lower electrode layer conductive material 14a is placed on the lower punch 3, the partition block 4 is placed thereon, the sintered material 10 is placed thereon, and the upper electrode conductive material 14b is placed thereon. Put.

  Next, as shown in FIG. 4B, when the upper punch 2 is moved downward, the softened sintered material 10 and the upper electrode conductive material 14 b are pushed into the partition block 4.

  By this pushing force, first, the upper electrode conductive material 14b is joined to the softened sintered material 10, and at the same time, the sintered material 10 is sheared together with the upper electrode conductive material 14b by the separator 4a. The lower electrode layer conductive material 14a is also sheared by the partition plate 4a. Then, the lower electrode layer conductive material 14a is joined to the sheared sintered material 10 by the pushing force at the lowest position of the upper punch 2, and separated into a large number of chip-like elements 11. Become so.

  Thereafter, the chip-shaped element 11 separated in the partition block 4 is cooled and cured in the chamber 1, and the cured chip-shaped element 11 is taken out of the chamber 1 together with the partition block 4 to obtain the third embodiment. As shown in FIGS. 3C and 3D, the chip-shaped elements (thermoelectric conversion elements) 11 with the electrode layers 14 a and 14 b are extruded by extruding each chip-shaped element 11 from the separation block 4 using the extrusion jig 5. Can be manufactured.

  According to the manufacturing method of the modified example of the third embodiment, in addition to the effects of the first and third embodiments, the lower electrode layer conductive material 14a is not easily subjected to the shearing force by the partition block 4, so The deformation due to the pushing force of the conductive material 14a is reduced, and the yield of the chip-like elements (thermoelectric conversion elements) 11 with the electrode layers 14a and 14b is improved.

  FIG. 5 is a manufacturing process diagram of the thermoelectric conversion element of the fourth embodiment. The structure of a hot press is the same as 1st Embodiment, and the process of manufacturing the sintered material 10 for thermoelectric conversion elements is also the same. Further, the third embodiment basically includes common steps.

  In the fourth embodiment, as shown in FIG. 5A, the lower electrode layer conductive material 14 a, the sintered material 10, and the upper electrode conductive material 14 b are placed in the chamber 1, and the lower punch 3 The lower electrode layer conductive material 14a is placed on the partition block 4 placed above, the sintered material 10 is placed thereon, and the upper electrode conductive material 14b is placed thereon.

  The conductive material 14a for the lower electrode layer and the conductive material 14b for the upper electrode are each processed in advance with the unevenness 14c on the opposing surface of the sintered material 10. The unevenness 14c can be applied by an etching process or a roughening process by polishing.

  5B, when the upper punch 2 is moved downward, the lower electrode layer conductive material 14a, the softened sintered material 10 and the upper electrode conductive material 14b are separated into the partition block 4. Pushed in.

  The lower electrode layer conductive material 14a and the upper electrode conductive material 14b are joined to the softened sintered material 10 by the pushing force, and at the same time, the sintered material 10 is used for the lower electrode layer by the partition plate 4a. It is sheared together with the conductive material 14 a and the upper electrode conductive material 14 b so as to be separated into a large number of chip-like elements 11.

  Thereafter, the chip-shaped element 11 separated in the partition block 4 is cooled and cured in the chamber 1, and the cured chip-shaped element 11 is taken out from the chamber 1 together with the partition block 4, and FIG. As shown in (d), the chip-like elements (thermoelectric conversion elements) 11 with the electrode layers 14a and 14b can be manufactured by extruding each chip-like element 11 from the separation block 4 using the extrusion jig 5. Become.

  According to the manufacturing method of the fourth embodiment, in addition to the effects of the third embodiment, the bonding area between the electrode layers 14a and 14b and the chip-like element 11 increases due to the processing of the projections and recesses 14c, and thus the electrode layers 14a and 14b. And the adhesion strength between the chip-like element 11 are further improved.

  FIG. 6 is a manufacturing process diagram of the thermoelectric conversion element of the fifth embodiment. The structure of a hot press is the same as 1st Embodiment, and the process of manufacturing the sintered material 10 for thermoelectric conversion elements is also the same. Further, the third embodiment basically includes common steps.

  In the fifth embodiment, as shown in FIG. 6A, in the chamber 1, the lower electrode layer conductive powder material 14a ', the partition block 4, the sintered material 10, and the upper electrode conductive powder material 14b' The lower electrode layer conductive powder material 14a 'is placed on the lower punch 3, the partition block 4 is placed thereon, the sintered material 10 is placed thereon, and the upper electrode conductive material is placed thereon. Place powder material 14b '.

  Next, as shown in FIG. 6B, when the upper punch 2 is moved downward, the conductive powder material 14b ′ for the upper electrode layer is sintered with the softened sintered material 10 by hot pressing. Thus, the conductive material 14b for the upper electrode layer is formed, and the sintered material 10 and the conductive material 14b for the upper electrode are pushed into the partition block 4.

  By this pushing force, first, the upper electrode conductive material 14b is joined to the softened sintered material 10, and at the same time, the sintered material 10 is sheared together with the upper electrode conductive material 14b by the separator 4a. become.

  Further, the conductive powder material 14a ′ for the lower electrode layer is sheared (separated) by the partition plate 4a, and between the sintered material 10 sheared by hot pressing at the lowest movement position of the upper punch 2, By sintering the lower electrode layer conductive powder material 14a ′, the lower electrode layer conductive material 14a is formed, and the lower electrode conductive material 14a is joined to the sheared sintered material 10. Become so.

  Thereafter, as shown in FIGS. 6C and 6D, the chip-shaped elements 11 having the electrode layers 14a and 14b (thermoelectric conversion) are extruded by extruding each chip-shaped element 11 from the separation block 4 using the extrusion jig 5. Element) 11 can be manufactured.

  According to the manufacturing method of the fifth embodiment, in addition to the effects of the third embodiment, the conductive powder materials 14a ′ and 14b ′ are electrically conductive when sintered with the sintered material 10 by hot pressing. Since the powder materials 14a ′ and 14b ′ bite into the sintered material 10 like irregularities 14c, the bonding area between the electrode layers 14a and 14b and the chip-like element 11 increases, so the electrode layers 14a and 14b and the chip The adhesion strength with the element 11 is improved.

  FIG. 7 is a manufacturing process diagram of the thermoelectric conversion element of the sixth embodiment. Although this process can be utilized for the manufacturing process of 1st-5th embodiment, what used the sintered material 10 with the electrode layer plating 13 of 2nd Embodiment is illustrated.

  As shown in FIG. 7A, the sintered material 10 with the electrode layer plating 13 is put in the vertically long chamber 1 and placed on the partition block 4 installed on the lower punch 3. Then, the partition plate 15 is placed on the sintered material 10, the partition block 4 is placed on the partition plate 15, and the sintered material 10 is placed on the partition block 4. By repeating the same process, a plurality of sets (four sets in this example) of the sintered materials 10 are stacked.

  Next, as shown in FIG. 7B, when the upper punch 2 is moved downward, the sintered material 10 with the electrode layer plating 13 of each layer is pushed into the partition block 4 of each layer, and the electrode layer is used by the partition plate 4a. It is sheared together with the plating 13 and separated into a large number of chip-like elements 11 in each layer.

  Thereafter, the chip-like element 11 separated in the separation block 4 is cooled and cured in the chamber 1, and the cured chip-like element 11 is taken out of the chamber 1 together with the separation block 4, and FIG. Referring to (d), the chip-shaped element (thermoelectric conversion element) 11 with the electrode layer 13 can be manufactured by extruding each chip-shaped element 11 from the separation block 4 of each layer using the extrusion jig 5. become.

  According to the manufacturing method of the sixth embodiment, since the sintered material 10 with the electrode layer plating 13 is laminated, the number of chip-like elements 11 that can be manufactured in one step is greatly increased, and thus the production efficiency is increased. To improve.

  FIGS. 8A and 8B show a chip-like element (thermoelectric conversion element) 11 with electrode layers 14a and 14b manufactured in the process of the third embodiment, and the characteristic point is the electrode layers 14a and 14b. Is a conductive mesh plate. Here, the mesh plate is a sheet having a shape in which a linear conductive material is knitted.

  Thus, if the chip-like element (thermoelectric conversion element) 11 with the electrode layers 14a and 14b, which are conductive mesh plates, the bonding area between the electrode layers 14a and 14b and the chip-like element 11 is increased. The adhesion strength between the electrode layers 14a and 14b and the chip-like element 11 is further improved.

  The chip-shaped element (thermoelectric conversion element) 11 with the electrode layers 14a and 14b, which is such a conductive mesh plate, is not limited to the one manufactured in the process of the third embodiment, and is manufactured by another manufacturing method. Needless to say, you can.

  The chip-like elements (thermoelectric conversion elements) 11 with the electrode layers 14a and 14b are arranged by arranging a total of 16 chip-like elements 11 in, for example, four rows and columns, as shown in FIGS. Then, the electrode layer 14a is electrically connected to the lower electrode circuit 17a of the lower substrate 17, and the electrode layer 14b is electrically connected to the upper electrode circuit 18a of the upper substrate 18, so that P-type and N-type thermoelectric conversions are performed. The elements 11 can be unitized by alternately electrically connecting them in series. In FIG. 8D, illustration of the electrode layers 14a and 14b and the electrode circuits 17a and 18a is omitted.

It is a manufacturing process figure of the thermoelectric conversion element of a 1st embodiment. It is a manufacturing-process figure of the thermoelectric conversion element of 2nd Embodiment. It is a manufacturing process figure of the thermoelectric conversion element of 3rd Embodiment. It is a manufacturing process figure of the thermoelectric conversion element of the modification of 3rd Embodiment. It is a manufacturing process figure of the thermoelectric conversion element of 4th Embodiment. It is a manufacturing process figure of the thermoelectric conversion element of 5th Embodiment. It is a manufacturing process figure of the thermoelectric conversion element of 6th Embodiment. A chip-shaped element with an electrode layer, which is a conductive mesh plate, (a) is a side view, (b) is a perspective view, and (c) is a plurality of chip-shaped elements with electrode layers arranged vertically and horizontally. The side view of the unit of a thermoelectric conversion element, (d) is a schematic perspective view of (c). (A) is a perspective view of the manufacturing apparatus of the thermoelectric conversion element of 1st Embodiment, (b) is a perspective view of the manufacturing apparatus of the thermoelectric conversion element of 2nd Embodiment, (c) is the principal part of the partition plate of a partition block It is sectional drawing.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Chamber 2 Upper punch 3 Lower punch 4 Separation block 4a Separation plate 5 Extrusion jig 10 Sintered material 11 Chip-shaped element (thermoelectric conversion element)
13 Electrode layer plating 14a, 14b Electrode layer 14c Concavity and convexity 15 Partition plate

Claims (4)

Producing a sintered material having a predetermined shape for a thermoelectric conversion element;
A step of performing electrode layer plating on at least one of the front and back surfaces of the sintered material;
A method of manufacturing a thermoelectric conversion element, comprising: pressing the sintered material subjected to the electrode layer plating into a partition block divided into chip-like element sizes to separate the chip-like element. Producing a sintered material having a predetermined shape for a thermoelectric conversion element;
A step of bonding an electrode layer to at least one of the front and back surfaces of the sintered material;
A method of manufacturing a thermoelectric conversion element, comprising: a step of pressing the sintered material bonded with the electrode layer into a partition block divided into chip-like element sizes to separate the chip-like element. The method for manufacturing a thermoelectric conversion element according to claim 2 , further comprising a step of forming irregularities on the opposing surface of the sintered material before joining the electrode layers. The method of manufacturing a thermoelectric conversion element according to claim 2, wherein the joining of the electrode layers includes a step of sintering and forming a conductive powder material.

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