JP6003442B2 - Thermoelectric device and manufacturing method thereof - Google Patents

Description

  The present invention relates to a thermoelectric device and a method for manufacturing the thermoelectric device, for example, a thermoelectric device formed using a flexible base material and a method for manufacturing the thermoelectric device.

  A thermoelectric device is basically a device that is formed from a series connection body of a large number of P-type semiconductors and N-type semiconductors, and generates electric power by applying a temperature difference to these semiconductor portions. In such a thermoelectric device, conventionally, a thermoelectric device manufactured by utilizing a flexible base material has been proposed.

For example, as shown in FIG. 29, an N-type thermoelectric material film 82 and a P-type thermoelectric material film 83 are alternately electrically connected in series in the extending direction of the base material 81 on an elongated flexible base material 81, It arrange | positions so that it may become thermally parallel in the width direction. A method of realizing a thermoelectric device by bending the base material 81 or winding it into a cylindrical shape is shown (for example, see Patent Document 1). Reference numeral ₈₄ 1, 84 ₂ are heat transfer plate.

  An advantage of a thermoelectric device manufactured by utilizing such a flexible base material is that a large number of connection portions connecting thermoelectric materials can be formed in a film. Also, taking advantage of the flexibility of the base material, the base material itself can be deformed even after film formation of a thermoelectric material or wiring, and a device shape with a relatively high degree of freedom can be formed. There are also advantages.

  However, in a thermoelectric device, a large number of P-type thermoelectric material films and N-type thermoelectric material films are electrically connected in series, and if they do not conduct even at one location, the series connection is disconnected, so that the function as a thermoelectric device cannot be performed. . Therefore, in order to realize high reliability as a thermoelectric device, one of the important points is how to form a connection between a large number of wirings and thermoelectric elements so as not to break down.

JP 2006-086510 A

  The thermoelectric device manufactured using the above-described flexible base material has a belt-like base material shape, and therefore the belt-like base material can be rolled up into a cylinder or a prism. However, it cannot be rolled up into a truncated cone. That is, there is a problem that the thermoelectric device having a shape having different cross-sectional areas on the high temperature side and the low temperature side cannot be finished.

  Further, as shown in FIG. 30 (a), as one application example of a thermoelectric device using a flexible base material, it is assumed to be wound around the surface of a pipe 91 through which a fluid or gas flows. . For example, as a high-temperature fluid or gas flows through the pipe 91, heat dissipation from the pipe surface occurs, and a temperature difference occurs in the longitudinal direction of the pipe 91. When electricity is generated using this temperature difference, the thermoelectric device in which the N-type thermoelectric material film 82 / P-type thermoelectric material film 83 are alternately electrically connected in series on the flexible substrate 81 as described above. 80 may be wound around the surface of the pipe 91.

  However, such a pipe through which a fluid or gas flows is not limited to a straight shape having a constant diameter. In general, there are pipes that connect pipes with different diameters, and the joints have relatively complicated shapes. In particular, in the case of a straight shape with a constant diameter, an exterior such as a heat insulating agent is often provided.

  On the other hand, the joint portion and the valve portion are not provided with such an exterior, and the outer shape is often exposed to the outside. That is, when the base material has a strip shape as in the conventional example, there is a problem that the use range is narrowed.

  In addition, in the connection portion 93 having a different diameter of the pipe 92 as shown in FIG. 30B, for example, the pipe 92 in which high-pressure gas flows adiabatically expands, so that a rapid temperature change is likely to occur. That is, the temperature difference is often greater than that of a simple straight portion. Therefore, if there is a thermoelectric device that can cope with such a non-straight portion, the amount of power generation can be expected to increase further.

  Therefore, even if a thermoelectric device using a flexible base material is used, it is expected that the thermoelectric device that can form a more flexible shape than the conventional one will be further spread. It is. Moreover, in manufacturing such a thermoelectric device, it is necessary to be able to manufacture at the same manufacturing cost as the conventional one or less.

  Accordingly, it is an object of the present invention to make it possible to manufacture a more flexible structure at a manufacturing cost equal to or lower than that of a conventional thermoelectric device.

From one aspect to be disclosed, a strip-shaped insulating base material having flexibility, and one end portion provided at a predetermined interval on the insulating base material is divided by an open end slit and the slit. A thermoelectric device comprising a thermoelectric material film element provided in a region and a wiring for electrically connecting adjacent thermoelectric material film elements in series is provided.

  Further, from another aspect to be disclosed, a step of providing first slits at a predetermined interval on a flexible strip-shaped first insulating base material, and a flexible strip-shaped second insulating property A step of providing second slits on the substrate at the same interval as the first slit, and an area divided by the first slit and an area divided by the second slit are alternately switched up and down. A step of superimposing the first insulating base material and the second insulating base material; and the first surface of the exposed both surfaces of the superposed first insulating base material and second insulating base material. Forming a first thermoelectric material film by forming a first conductive type thermoelectric material by removing every other portion of the slits and the vicinity of the second slit, and the superposed first insulating property After separating the base material and the second insulating base material, the region divided by the first slit and the first A step of superimposing the first insulating base material and the second insulating base material so that the vertical relationship of the regions divided by the slits is reversed, and the superposed first insulating base material The second conductivity type is opposite to the first conductivity type except for the vicinity of the first slit and the second slit on both exposed surfaces of the material and the second insulating substrate. Forming a thermoelectric material to form a second thermoelectric material film; separating the first insulating base material from the second insulating base material; and the first insulating base material. The first thermoelectric material film and the second thermoelectric material film formed in the region divided by the first slit are connected to each other at one end side thereof and adjacent to each other at the other end side. Forming a wiring electrically connected in series with a reverse conductivity type thermoelectric material film formed in a region In the second insulating substrate, the first thermoelectric material film and the second thermoelectric material film formed in the region divided by the second slit are connected to each other at one end side. A method of manufacturing a thermoelectric device, comprising: forming a wiring electrically connected in series with a reverse conductivity type thermoelectric material film formed in a segmented region adjacent to the other end side. The

  According to the disclosed thermoelectric device and the manufacturing method thereof, a more flexible structure can be manufactured at a manufacturing cost that is the same as or lower than the conventional one.

It is explanatory drawing of the thermoelectric device of embodiment of this invention. It is a top view which shows an example of the insulating base material used for the manufacturing process of the thermoelectric device of embodiment of this invention. It is a schematic plan view of the thermoelectric device of Example 1 of the present invention. It is explanatory drawing to the middle of the manufacturing process of the thermoelectric device of Example 1 of this invention. It is explanatory drawing to the middle after FIG. 4 of the manufacturing process of the thermoelectric device of Example 1 of this invention. It is explanatory drawing to the middle after FIG. 5 of the manufacturing process of the thermoelectric device of Example 1 of this invention. It is explanatory drawing to the middle after FIG. 6 of the manufacturing process of the thermoelectric device of Example 1 of this invention. It is explanatory drawing to the middle after FIG. 7 of the manufacturing process of the thermoelectric device of Example 1 of this invention. It is explanatory drawing to the middle after FIG. 8 of the manufacturing process of the thermoelectric device of Example 1 of this invention. It is explanatory drawing to the middle after FIG. 9 of the manufacturing process of the thermoelectric device of Example 1 of this invention. It is explanatory drawing to the middle after FIG. 10 of the manufacturing process of the thermoelectric device of Example 1 of this invention. It is explanatory drawing to the middle after FIG. 11 of the manufacturing process of the thermoelectric device of Example 1 of this invention. It is explanatory drawing after FIG. 12 of the manufacturing process of the thermoelectric device of Example 1 of this invention. It is explanatory drawing of the actual usage example of the thermoelectric device of Example 1 of this invention. It is structure explanatory drawing at the time of winding up a thermoelectric device by using the conventional strip-shaped tape as a base material. It is explanatory drawing to the middle of the manufacturing process of the thermoelectric device of Example 2 of this invention. It is explanatory drawing to the middle after FIG. 16 of the manufacturing process of the thermoelectric device of Example 2 of this invention. It is explanatory drawing to the middle after FIG. 17 of the manufacturing process of the thermoelectric device of Example 2 of this invention. It is explanatory drawing to the middle after FIG. 18 of the manufacturing process of the thermoelectric device of Example 2 of this invention. It is explanatory drawing to the middle after FIG. 19 of the manufacturing process of the thermoelectric device of Example 2 of this invention. It is explanatory drawing to the middle after FIG. 20 of the manufacturing process of the thermoelectric device of Example 2 of this invention. It is explanatory drawing after FIG. 21 of the manufacturing process of the thermoelectric device of Example 2 of this invention. It is a top view of the thermoelectric device of Example 3 of this invention. It is explanatory drawing of the usage example of the thermoelectric device of Example 3 of this invention. It is explanatory drawing to the middle of the manufacturing process of the thermoelectric device of Example 3 of this invention. It is explanatory drawing after FIG. 25 of the manufacturing process of the thermoelectric device of Example 3 of this invention. It is explanatory drawing of the manufacturing process of the thermoelectric device of Example 4 of this invention. It is a top view of the thermoelectric device of Example 5 of this invention. It is a perspective view of the thermoelectric device using the conventional flexible base material. It is explanatory drawing of the usage example of the thermoelectric device using the conventional flexible base material.

  Here, with reference to FIG. 1, the thermoelectric device of embodiment of this invention is demonstrated. FIG. 1 is an explanatory view of a thermoelectric device according to an embodiment of the present invention. FIG. 1 (a) is a plan view of the thermoelectric device with a slit inserted from one side, and FIG. It is a top view at the time of putting.

As shown in the figure, slits 12 ₁ and 12 ₂ are inserted into a strip-shaped insulating base material 11 having flexibility at regular intervals, and a thermoelectric material film element 13 is formed in a region divided by the slits 12 ₁ and 12 _{2. 1,} 13 ₂ provided. Next, the wiring 14 that bypasses the slits 12 ₁ and 12 ₂ is formed so that the thermoelectric material film elements 13 ₁ and 13 ₂ are electrically connected in series.

If thermoelectric material film element 13 ₁ and the thermoelectric material film element 13 ₂ is the same as the thermoelectric material, one region partitioned by the slit 12 _1, 12 ₂ is one thermoelectric unit. Further, if the thermoelectric material film element 13 ₁ and the thermoelectric material film element 13 ₂ is the inverse of the thermoelectric material conductivity type from each other, form one thermoelectric unit in two regions divided by the slit 12 _1, 12 _2.

  The insulating base material 11 having flexibility is typically polyimide, but a resin film having the same flexibility can be used. As such examples, for example, Kapton, polycarbonate, polyethylene, polyethylene terephthalate (PET), polysulfone (PSF), polyether ethyl ketone (PEEK), polyphenylene sulfite (PPS) and the like can be used. The selection method of these base materials includes whether or not the film formation conditions (temperature, degassing) of the thermoelectric material are met, whether or not the use conditions of the device are met, and whether or not the desired cost conditions are met. Or so.

As the thermoelectric material, a BiTe alloy such as Bi ₂ Te ₃ is typical as an N-type thermoelectric material, and a BiTe alloy such as Bi _0.3 Sb _1.7 Te ₃ is typical as a P-type thermoelectric material. However, other BiTe systems (BiTe, SbTe, BiSe and their compounds) may be used. Further, chromel containing Ni and Cr as main components may be used as the P-type thermoelectric material, and constantan containing Cu and Ni as main components may be used as the N-type thermoelectric material.

Alternatively, PbTe system (PbTe, SnTe, AgSbTe, GeTe and their compounds), Si-Ge system (Si, Ge, SiGe), silicide system (FeSi, MnSi, CrSi), skutterudite system (MX ₃ , or RM) ₄ X ₁₂ represents a compound, where M = Co, Rh, Ir, X = As, P, Sb, R = La, Yb, Ce)), transition metal oxide system (NaCoO , CaCoO, ZnInO, SrTiO, BiSrCoO, PbSrCoO, CaBiCoO, BaBiCoO), zinc antimony (ZnSb), boron compounds (CeB, BaB, SrB, CaB, MgB, VB, NiB, CuB, LiB), cluster solid (B cluster) , Si cluster, C cluster, AlRe, AlReSi), Of zinc (ZnO), it may also be used such as carbon nanotubes.

As a thermoelectric material film elements 13 _1, 13 ₂ of the film forming method is a sputtering method is typically not limited to this, for example, vapor deposition method, CVD method, plating method, such as aerosol deposition A film forming method may be used.

As a method of forming the slits 12 ₁ and 12 _2, a tool such as a cutter or scissors may be used depending on the size, or a method of punching a slit mold in advance may be used. Alternatively, fine slits may be formed by laser processing such as CO ₂ laser or ultrasonic processing.

  The wiring 14 is preferably made of a material having a very low resistivity as compared with a thermoelectric material such as Al or Cu. As a point of concern in the structure of the present invention with respect to the conventional structure, there is a point that a part of the wiring 14 that connects the thermoelectric material film elements circumvents the cut, resulting in an increase in length.

  However, in a thermoelectric device formed from a film-like thermoelectric material film, the amount of electric power generated due to a temperature difference is at most mW level, so that the current flowing through the wiring is small and the length of the wiring is long. The exothermic effect caused by this is negligible.

FIG. 2 is a plan view showing an example of an insulating substrate used in the manufacturing process of the thermoelectric device according to the embodiment of the present invention. As shown in the figure, two different types of first insulating base material 21 ₁ and second insulating base material 21 ₂ are prepared, and the first slit 22 ₁ and the second slit are respectively provided at the same pitch. 22 ₂ is formed.

In the first insulating base material 21 ₁ and the second insulating base material 21 ₂ , the region divided by the first slit 22 ₁ and the region divided by the second slit 22 ₂ are alternately switched up and down. Overlapping so that. By depositing the thermoelectric material in this state, it is possible to form twice as many elements as the conventional one by depositing the P-type thermoelectric material and the N-type thermoelectric material once.

  As a result, it is possible to reduce the cost required for film formation of the thermoelectric material, which is considered to be the highest in terms of manufacturing cost, to 1/2. Further, in this manufacturing method, a metal mask is not necessarily required when forming a thermoelectric material, and a disposable seal or a resist pattern may be used as a mask. In FIG. 2, an example of 2: 1 is shown, but it may be 1: 1 or n: 1 (n is an integer).

  As described above, in the embodiment of the present invention, since the slits are formed between the individual thermoelectric material film elements from a certain direction, it is possible to stick to a curved surface more flexible than in the past, and the degree of freedom. A thermoelectric device having a high shape can be formed.

Next, a thermoelectric device according to Example 1 of the present invention will be described with reference to FIGS. FIG. 3 is a schematic plan view of the thermoelectric device according to the first embodiment of the present invention. Here, a thermoelectric device 30 formed from a type 1 sheet described later will be described as an example. As shown in the figure, the polyimide sheet 31 ₁ is provided with slits 32 ₁ at regular intervals, and an N-type thermoelectric material film element 52 ₁ and a P-type thermoelectric material film are formed in a region divided by the slits 32 _1. element 54 ₁ are alternately provided. Then, the electrode patterns 33 ₁ are provided so that this N-type thermoelectric material film element 52 ₁ and the P-type thermoelectric material film element 54 ₁ are sequentially electrically connected in series.

In the thermoelectric device according to the first embodiment of the present invention, since the slit 32 ₁ is provided in the belt-shaped polyimide sheet 31 ₁ , the degree of freedom of deformation when winding is increased, and a bent or tapered member can be formed. Easy to install.

Next, with reference to FIG. 4 thru | or FIG. 13, the manufacturing process of the thermoelectric device of Example 1 of this invention is demonstrated. First, as shown in FIG. 4 (a), providing a polyimide sheet ₃₁ 1, 31 ₂ and the polyimide sheet 41 of the type 2 Type 1. Polyimide sheet ₃₁ 1, 31 ₂ is the thickness of the type 1 is 25 [mu] m, a length to width 5.9mm at 20 cm. In the polyimide sheets 31 ₁ and 31 ₂ , slits 32 ₁ and 32 ₂ having a width of 0.2 mm and a length of 2.75 mm are formed from both sides in the width direction at a pitch of 2.2 mm.

On the other hand, the type 2 polyimide sheet 41 has a thickness of 25 μm, a length of 20 cm, and a width of 12 mm. In this polyimide sheet 41, two rows of slits 42 having a length of 5.6 mm and a width of 0.2 mm that are not opened at the end in the width direction are formed at a pitch of 2.2 mm. The slits 32 ₁ , 32 ₂ , 42 are formed by punching.

Then, as shown in FIG. 5 (b), the upper with respect to each slit 42 of the polyimide sheet 41 every one polyimide sheet 31 _1, 31 ₂ - Insert as dive alternately below, a slit 42 The slits 32 ₁ and 32 ₂ are aligned with each other. At the time of insertion, a plate-like member (not shown) that is bent in an arc shape is used to facilitate insertion.

  FIG. 6C is a plan view after insertion. Next, as shown in FIG. 6D, a disposable seal having a width of 0.8 mm is used as a mask 51 and is attached to the electrode formation region.

  Next, as shown in FIG. 7E, an N-type thermoelectric material film 52 having a thickness of 5 μm is formed by sputtering. Here, an N-type BiTe alloy is used as the N-type thermoelectric material film 52. In the figure, the N-type thermoelectric material film deposited on the mask 51 is not shown for easy understanding of the situation. Next, as shown in FIG. 7F, the mask 51 is removed.

Then, as shown in FIG. 8 (g), after withdrawal of the polyimide sheet ₃₁ 1, 31 _2, again, upper every one polyimide sheet ₃₁ 1, 31 ₂ for each slit 42 of the polyimide sheet 41 - Insert the lower side alternately. However, at this time, it is inserted so that the vertical relationship is reversed with respect to FIG. 5B and aligned so that the slit 42 and the slits 32 ₁ and 32 ₂ coincide.

  FIG. 9 (h) is a plan view after insertion. Next, as shown in FIG. 9I, a disposable seal having a width of 0.8 mm is attached to the electrode formation region as a mask 53.

  Next, as shown in FIG. 10J, a P-type thermoelectric material film 54 having a thickness of 5 μm is formed by sputtering. Here, a P-type BiSbTe alloy is used as the P-type thermoelectric material film 54. In the figure, the P-type thermoelectric material film deposited on the mask 53 is not shown for easy understanding of the situation. Next, as shown in FIG. 10K, the mask 53 is removed.

Next, as shown in FIG. 11 (l), two sheets of type 1 in which N-type thermoelectric material films 52 and P-type thermoelectric material films 54 are alternately provided in a stripe pattern by pulling out the polyimide sheets 31 ₁ and 31 _2. Thus, a total of three sheets are obtained, one sheet of type 2 and one sheet of type 2.

Next, as shown in FIG. 12 (m), an aluminum film having a thickness of 0.1 μm is formed on each sheet using a mask vapor deposition method to form electrode patterns 33 ₁ , 33 ₂ , 43. At this time, as described later, when the electrode patterns 33 ₁ , 33 ₂ , 43 are separated into individual thermoelectric devices, each N-type thermoelectric material film element 52 ₁ and each P-type thermoelectric material film element 54 ₁ A pattern connected in series. Also, the mutual connection of the thermoelectric unit comprising a single N-type thermoelectric material film elements 52 ₁ and one of the P-type thermoelectric material film element 54 _1, the slits 32 _1, 32 _2, 42 of serpentine shape along the edge of the A pattern. Since a large current does not flow through the thermoelectric device, it is sufficient that the electrode patterns 33 ₁ , 33 ₂ , and 43 have a thickness of about 0.1 μm.

  Next, as shown in FIG. 13 (n), a total of four thermoelectric devices 30 are obtained by cutting the two type 1 sheets into two along the longitudinal center line. On the other hand, by cutting the type 2 sheet into four equal parts along the length direction, a total of four thermoelectric devices 40 are obtained, and a total of eight thermoelectric devices are obtained.

  As described above, in Example 1 of the present invention, the number of elements twice as many as that in the conventional manufacturing method can be formed by forming the P-type thermoelectric material and the N-type thermoelectric material once. In addition, in a thermoelectric device made of a thermoelectric material formed on a substrate, it is desirable that the film thickness is as thick as possible in order to reduce the resistance of the thermoelectric material. In general, there is an example in which a thick film having a thickness of 10 μm is formed as a product. That is, it is considered that the film formation time is considerably long. As can be inferred from this, the film formation cost of the thermoelectric material occupies the manufacturing cost of this type of thermoelectric device. Therefore, when the structure and the manufacturing method of Example 1 of the present invention are used, the film formation cost of the thermoelectric material can be reduced to about ½, which has the effect of greatly reducing the manufacturing cost of the entire thermoelectric device.

  Further, when a thick film is formed using, for example, a metal mask, the metal mask is often clogged, and the metal mask is heavily cleaned and consumed. In the case of using the structure and manufacturing method of Example 1 of the present invention, a mask dedicated to the thermoelectric material is not necessary, so that such a problem is unlikely to occur, and the waste of the thermoelectric material can be eliminated. As an effect, the manufacturing cost is reduced.

FIG. 14 is an explanatory diagram of an actual use example of the thermoelectric device according to the first embodiment of the present invention. First, as shown in FIG. 14A, a heat insulating tape 55 having a wedge-shaped cross section is used. The thermoelectric device 30 (40) is wound up. At this time, the side with the open end of the slit 32 ₁ (32 ₂ , 42) is aligned with the direction in which the cross section of the heat insulating tape 55 is thick (the upper side in the drawing).

FIG. 14B is a perspective view of the rolled thermoelectric device 30 (40), and has a truncated cone shape. Then, Figure 14 (c), the thermoelectric device 30 (40) of the bottom and top surface having good thermal conductivity insulating disc ₅₆ 1, 56 ₂ and the installation, large insulating disc 56 _first diameter A metal fin 57 is installed on the top. Here, as with good thermal conductivity insulating disc 56 _1, 56 _2, using a metal disc to the aluminum surface was alumina treated with material, also metal fins 57 also utilizes the same material.

  FIG. 15 is an explanatory diagram of a configuration when a thermoelectric device is wound up using a conventional belt-like tape as a base material, and FIG. 15A is a perspective view of the wound state, and one side of the polyimide sheet 31 is an open end. Since no slit is provided, it becomes a cylindrical shape. FIG.15 (b) is a perspective view at the time of installing an insulating disc and a metal fin similarly to FIG.14 (c).

  Such a thermoelectric device is used by placing the lower surface of the device in close contact with a surface hotter than room temperature, for example, a boiler surface or a car engine surface, and generating a temperature difference by heat radiation from the metal fins. In other words, a method of using power generation from a temperature difference between a high temperature surface and room temperature can be considered.

  In this case, it is desired to increase the heat dissipation from room temperature to increase the temperature difference and increase the amount of power generation, but by increasing the area on the heat dissipation side as shown in FIG. The temperature difference between the bottom surface side and the top surface side increases, and the amount of power generation increases. In addition, the greater the surface area of the insulating disk on the top surface side, the greater the degree of design freedom for installing the metal fins. Moreover, even when the same number of metal fins are installed, if the area of the insulating disk on the top surface side is increased, the spacing between the metal fins can be increased, and this also increases the heat dissipation efficiency.

Next, the thermoelectric device according to the second embodiment of the present invention will be described with reference to FIGS. 16 to 22. However, since the final structure is the same as that of the first embodiment, the manufacturing process will be described here. To do. First, as shown in FIG. 16A, two polyimide sheets 61 ₁ and 61 ₂ having the same shape are prepared. Here, the thickness of the polyimide sheets 61 ₁ and 61 ₂ is 25 μm, the length is 20 cm, the width is 3 mm, and the slits 62 ₁ and 62 ₂ having a width of 0.2 mm and a length of 2.6 mm are arranged at a pitch of 2.2 mm. Form by punching. Here, for easy understanding of the process, the two polyimide sheets 61 ₁ and 61 ₂ are indicated by different hatching.

Then, as shown in FIG. 17 (b), and lift alternately every one classified partial slit ₆₂ 1, 62 _2, superimposed insert the polyimide sheet 61 ₁ and the polyimide sheet 61 ₂ to each other. FIG. 17C is a plan view showing the superimposed state.

  Next, as shown in FIG. 18D, a disposable seal having a width of 0.8 mm is attached as a mask 63 to the electrode formation region. Next, as shown in FIG. 18E, an N-type thermoelectric material film 64 having a thickness of 5 μm is formed by sputtering. Here, an N-type BiTe alloy is used as the N-type thermoelectric material film 64. In the figure, the N-type thermoelectric material film deposited on the mask 63 is not shown for easy understanding of the situation. Next, as shown in FIG. 18F, the mask 63 is removed.

Next, as shown in FIG. 19G, the polyimide sheets 61 ₁ and 61 ₂ are pulled out. Next, as shown in FIG. 19 (h), _every other part divided by the slits 62 ₁ and 62 ₂ is alternately lifted upside down so that it is upside down from the case of FIG. 17 (b), superimposed insert the polyimide sheet 61 ₁ and the polyimide sheet 61 ₂ to each other. FIG. 20 (i) is a plan view showing a superimposed state.

  Next, as shown in FIG. 20 (j), a disposable seal having a width of 0.8 mm is attached as a mask 65 to the electrode formation region. Next, as shown in FIG. 20K, a P-type thermoelectric material film 66 having a thickness of 5 μm is formed by sputtering. Here, a P-type BiSbTe alloy is used as the P-type thermoelectric material film 66. In the figure, the P-type thermoelectric material film deposited on the mask 65 is not shown for easy understanding of the situation.

Next, as shown in FIG. 21L, the mask 65 is removed. Next, as shown in FIG. 21 (m), by pulling out the polyimide sheets 61 ₁ and 61 ₂ , _two sheets in which the N-type thermoelectric material film 64 and the P-type thermoelectric material film 66 are alternately provided in stripes are obtained. can get.

Next, as shown in FIG. 22 (n), an aluminum film having a thickness of 0.1 μm is formed on each sheet using a mask vapor deposition method to form electrode patterns 67 ₁ and 67 ₂ .

  Thus, in Example 2 of this invention, it is not necessary to cut a sheet | seat in the last process. Moreover, the method of superimposing the base materials before film formation is simple, and the process is easy to automate. However, in order to form a film with a large area without waste using a sputtering apparatus, it is necessary to arrange a large number of two laminated strip-like insulating base materials in parallel.

Next, a thermoelectric device according to Example 3 of the present invention will be described with reference to FIGS. Figure 23 is a plan view of the thermoelectric device of the third embodiment of the present invention, although the basic configuration is the same as the thermoelectric device of Example 1, the slits from both sides in the width direction of the polyimide sheet 31 _1, 31 ₂ 32 ₃ , 32 ₄ , 32 ₅ , 32 ₆ are provided. Here, a type 1 sheet is described.

FIG. 24 is an explanatory diagram of a usage example of the thermoelectric device according to the third embodiment of the present invention. Since the slits 32 ₃ , 32 ₄ , 32 ₅ , and 32 ₆ are provided on both sides, the upper bottom surface side and the lower bottom surface side are provided. Since it can be spread on both sides, the degree of freedom of deformation is increased and the application range is widened. For example, as shown in the figure, a thermoelectric device can be wound around a bent portion of a pipe 58 through which a fluid or gas flows.

  Next, the manufacturing process of the thermoelectric device according to the third embodiment of the present invention will be described with reference to FIGS. 25 and 26, except that the slits are provided on both sides as described above. Since the film forming process is exactly the same, only the sheet overlapping process will be described.

First, as shown in FIG. 25, to prepare a polyimide sheet ₃₁ 1, 31 ₂ and the polyimide sheet 41 of the type 2 Type 1. Polyimide sheet ₃₁ 1, 31 ₂ is the thickness of the type 1 is 25 [mu] m, a length to width 5.9mm at 20 cm. In this polyimide seed, slits 32 ₃ and 32 ₄ having a width of 0.2 mm and a length of 2.25 mm are formed from both sides in the width direction at a pitch of 2.2 mm, and a slit having a length of 1 mm therebetween. 32 ₅ and 32 ₆ are formed. The slits 32 ₅ and 32 ₆ correspond to slits provided at the other end.

On the other hand, the type 2 polyimide sheet 41 has a thickness of 25 μm, a length of 20 cm, and a width of 12 mm. The polyimide sheet 41, a slit 42 ₁ width 4.6mm is not open at the edge in the width direction of 0.2mm are formed two rows at a pitch of 2.2mm in length. Further, the length between the slits 42 ₁ are slit 42 ₂ of 1mm is formed, is formed in length slit 42 ₃ 0.5mm on both sides in the width direction. Note that the slits 32 ₃ , 32 ₄ , 32 ₅ , 32 ₆ , 42 ₁ , 42 ₂ , and 42 ₃ are formed by punching.

Then, as shown in FIG. 26, upper with respect to each slit 42 ₁ of the polyimide sheet 41 every one polyimide sheet ₃₁ 1, 31 ₂ - Insert as dive alternately lower slits 42 ₁ and the slit Align so that 32 ₃ and 32 ₄ coincide. At the time of insertion, a plate-like member (not shown) that is bent in an arc shape is used to facilitate insertion. Thereafter, the same steps as those in the first embodiment may be performed.

  Thus, in Example 3 of this invention, since the slit is formed in both sides, the freedom degree of a deformation | transformation becomes high and an application range can be expanded.

  Next, a thermoelectric device according to a fourth embodiment of the present invention will be described with reference to FIG. 27. In this case, the basic manufacturing process is the same as the fourth embodiment described above except that slits are provided on both sides. Since the final structure is the same as that of the third embodiment, the process up to the sheet overlapping process will be described.

First, as shown in FIG. 27A, two polyimide sheets 61 ₁ and 61 ₂ having the same shape are prepared. Here, the polyimide sheet has a thickness of 25 μm, a length of 20 cm, and a width of 3 mm. In addition, slits 62 ₃ and 62 ₄ having a width of 0.2 mm and a length of 2 mm are formed by punching at a pitch of 2.2 mm, and slits 62 ₅ and 62 ₆ having a length of 0.5 mm are formed from the opposite direction. To do. Here, for easy understanding of the process, the two polyimide sheets 61 ₁ and 61 ₂ are indicated by different hatching.

Then, as shown in FIG. 27 (b), and lift alternately every one classified partial slit ₆₂ 3, 62 _4, superimposed insert the polyimide sheet 61 ₁ and the polyimide sheet 61 ₂ to each other. Thereafter, the same process as that of the second embodiment may be performed.

  Thus, in Example 4 of this invention, since the slit is formed in both sides, the freedom degree of a deformation | transformation becomes high and an application range can be expanded. Further, as in the second embodiment, it is not necessary to cut the sheet in the final process, and the method of superimposing the substrates before film formation is simple, so that the process can be easily automated.

  Next, with reference to FIG. 28, the thermoelectric device of Example 5 of this invention is demonstrated. FIG. 28 is a plan view of the thermoelectric device according to the fifth embodiment of the present invention. Here, the thermoelectric unit is formed only of the N-type thermoelectric material film. That is, slits 72 are formed in the polyimide sheet 71 at regular intervals, and an N-type BeTeN film having a thickness of 5 μm is formed in a region divided by the slits 72 to form an N-type thermoelectric material film 73.

  Next, by using a mask vapor deposition method, aluminum having a thickness of 0.1 μm is vapor-deposited to form an electrode pattern 74 that electrically connects the N-type thermoelectric material film 73 formed in the region divided by the slit 72 in series. To do. The N-type thermoelectric material film 73 formed in the region divided by the slit 72 becomes a thermoelectric unit.

  Depending on the type of thermoelectric material, it may be difficult to prepare both P-type and N-type thermoelectric materials having good characteristics. In Example 5 of the present invention, a thermoelectric device can be realized with only an N-type thermoelectric material by slightly changing the wiring layout.

  In addition, it may replace with N type thermoelectric material and may form a thermoelectric device only with P type thermoelectric material. Further, similarly to the third embodiment or the fourth embodiment, slits may be formed from both sides in the width direction of the strip-shaped insulating substrate.

  In each of the above embodiments, the sheets to be overlapped are formed of the same material, but sheets of different materials may be overlapped. In this case, two types of thermoelectric devices having different characteristics such as flexibility can be manufactured in a single manufacturing process.

Here, the following supplementary notes are attached to the embodiments of the present invention including Examples 1 to 5.
(Supplementary note 1) A flexible strip-shaped insulating base material, and one end portion provided at a predetermined interval on the insulating base material is provided in an open end slit and a region partitioned by the slit. A thermoelectric device comprising: a thermoelectric material film element formed; and a wiring that electrically connects the adjacent thermoelectric material film elements in series.
(Supplementary note 2) The thermoelectric device according to supplementary note 1, wherein the slit is inserted from both sides in the width direction of the insulating substrate.
(Additional remark 3) The thermoelectric device of Additional remark 1 or Additional remark 2 characterized by the N-type thermoelectric material film | membrane element and the P-type thermoelectric material film | membrane element being alternately provided in each area | region divided by the said slit.
(Supplementary note 4) The thermoelectric device according to supplementary note 1 or supplementary note 2, wherein only the N-type thermoelectric material film element or only the P-type thermoelectric material film element is provided in the region divided by the slit.
(Supplementary note 5) The thermoelectric device according to any one of supplementary notes 1 to 4, wherein the strip-shaped insulating base material provided with the thermoelectric material film element is wound in a truncated cone shape.
(Appendix 6) Insulating plate-like members are disposed on the upper and lower bottom surfaces of the thermoelectric device wound in the shape of the truncated cone, and a heat dissipation member is provided on the bottom surface having a large area among the upper and lower bottom surfaces. The thermoelectric device according to appendix 5, characterized in that:
(Supplementary note 7) The thermoelectric device according to supplementary note 6, wherein the insulating member is a metal member provided with an insulating film on a surface thereof.
(Additional remark 8) The process which provides a 1st slit at a fixed space | interval in the strip | belt-shaped 1st insulating base material which has flexibility, and said 1st to the strip | belt-shaped 2nd insulating base material which has flexibility. A step of providing a second slit at the same interval as the slit of the first insulating property so that the region divided by the first slit and the region divided by the second slit are alternately switched up and down. A step of superimposing the base material and the second insulating base material, and the first slit and the second slit on both exposed surfaces of the superposed first insulating base material and second insulating base material. Forming a first thermoelectric material film by forming a first thermoelectric material film by removing every other vicinity of the slit, and the superposed first insulating base material and second After separating the insulating base material, it is divided by the first slit and the second slit. Overlapping the first insulating base material and the second insulating base material so that the vertical relationship of the regions to be reversed is reversed, and the superposed first insulating base material and second A second conductive type thermoelectric material having a conductivity type opposite to that of the first conductivity type is formed by removing every other part of the insulating base in the vicinity of the first slit and the second slit. And forming the second thermoelectric material film, separating the first insulating substrate and the second insulating substrate, and the first insulating substrate. The first thermoelectric material film and the second thermoelectric material film formed in the region divided by the slits are connected to each other on one end side and formed on the adjacent divided region on the other end side. Forming a wiring electrically connected in series with the reverse conductivity type thermoelectric material film, and the second insulating property In the material, the first thermoelectric material film and the second thermoelectric material film formed in the region divided by the second slit are connected to each other on one end side thereof, and adjacent sections on the other end side Forming a wiring electrically connected in series with the reverse conductivity type thermoelectric material film formed in the formed region.
(Supplementary Note 9) The width of the first insulating base has a width corresponding to n times the width of the second insulating base, and the first slit is the first insulating base. N rows are formed in the width direction of the material, and in the step of superimposing the first insulating base material and the second insulating base material, n second insulating base materials are arranged in the first row of each row. 9. The method of manufacturing a thermoelectric device according to appendix 8, wherein the slits are alternately inserted and overlapped.
(Additional remark 10) The process which divides 2n the 1st insulating base material which formed the said wiring along the length direction, and the 2nd insulating material base material which formed the said wiring divided into 2 along the length direction The method of manufacturing a thermoelectric device according to appendix 9, further comprising a step of:
(Supplementary Note 11) The first insulating base and the second insulating base have the same planar structure, and the first slit and the second slit are slits whose one ends are opened. Yes, in the step of superimposing the first insulating base material and the second insulating base material, the region divided by the first slit and the region divided by the second slit alternately turn up and down. 9. The method of manufacturing a thermoelectric device according to appendix 8, wherein the slit is inserted from the open end side of the slit so as to be reversed.

11 Insulating Base Material 12 ₁ , 12 ₂ Slit 13 ₁ , 13 ₂ Thermoelectric Material Film Element 14 Wiring 21 ₁ First Insulating Base Material 21 ₂ Second Insulating Base Material 22 ₁ First Slit 22 ₂ Second slit 30 thermoelectric device 31 _1, 31 ₂ polyimide sheet ₃₂ 1-32 ₆ slits ₃₃ 1, 33 ₂ electrode pattern 40 thermoelectric device 41 polyimide sheet 42 _{1, 42} 2, 42 ₃ slits 43 electrode patterns 51 and 53 mask 52 N-type thermoelectric material film 52 ₁ N-type thermoelectric material film element 54 P-type thermoelectric material film 54 ₁ P-type thermoelectric material film element 55 heat insulating material tape ₅₆ 1, 56 ₂ insulating disc 57 metal fins 58 pipe ₆₁ 1, 61 ₂ polyimide sheets 62 _{1 to} 62 ₆ slits 63, 65 mask 64 N-type thermoelectric material film 66 P-type thermoelectric material film 67 ₁ , 67 ₂ electrode pad Turn 71 polyimide sheet 72 slit 73 N-type thermoelectric material film 74 electrode pattern 80 thermoelectric device 81 substrate 82 N-type thermoelectric material film 83 P-type thermoelectric material film ₈₄ 1, 84 ₂ heat transfer plate 91, 92 pipes 93 connecting portion

Claims (6)

A strip-shaped insulating base material having flexibility;
One end provided on the insulating substrate at regular intervals is an open-end slit,
A thermoelectric material film element provided in a region divided by the slit;
A thermoelectric device comprising: a wiring for electrically connecting adjacent thermoelectric material film elements in series.   The thermoelectric device according to claim 1, wherein the slit is inserted from both sides in the width direction of the insulating base material.   The thermoelectric device according to claim 1 or 2, wherein the strip-shaped insulating base material provided with the thermoelectric material film element is wound in a truncated cone shape. A step of providing first slits at regular intervals on a flexible strip-shaped first insulating substrate;
Providing a second slit at the same interval as the first slit on the flexible strip-shaped second insulating substrate;
The first insulating base material and the second insulating base material are overlapped so that a region divided by the first slit and a region divided by the second slit are alternately switched up and down. Process,
A thermoelectric material of the first conductivity type except for the vicinity of the first slit and the second slit on both exposed surfaces of the superimposed first insulating substrate and second insulating substrate. Forming a first thermoelectric material film by forming
After separating the superimposed first insulating base material and second insulating base material, the vertical relationship between the region divided by the first slit and the region divided by the second slit is reversed. Superimposing the first insulating substrate and the second insulating substrate so as to be,
What is the first conductivity type except for the vicinity of the first slit and the second slit on the exposed surfaces of the superposed first insulating base material and second insulating base material? Forming a second thermoelectric material film by forming a second conductivity type thermoelectric material of reverse conductivity type;
Separating the first insulating substrate and the second insulating substrate;
In the first insulating base material, the first thermoelectric material film and the second thermoelectric material film formed in the region divided by the first slit are connected to each other on one end side, and Forming a wiring electrically connected in series with a reverse conductivity type thermoelectric material film formed in an adjacent sectioned region on the other end side;
In the second insulating base material, the first thermoelectric material film and the second thermoelectric material film formed in the region divided by the second slit are connected to each other on one end side, and Forming a wiring electrically connected in series with a reverse conductivity type thermoelectric material film formed in an adjacent sectioned region on the other end side;
A method for manufacturing a thermoelectric device, comprising: The width of the first insulating substrate has a width corresponding to n times the width of the second insulating substrate;
N rows of the first slits are formed in the width direction of the first insulating substrate;
In the step of superimposing the first insulating base material and the second insulating base material, n pieces of the second insulating base materials are inserted so as to pass through the first slits in each row alternately. The method of manufacturing a thermoelectric device according to claim 4, wherein the superposition is performed. The first insulating substrate and the second insulating substrate have the same planar structure;
The first slit and the second slit are slits having one end opened,
In the step of superimposing the first insulating substrate and the second insulating substrate, the region divided by the first slit and the region divided by the second slit are alternately upside down. The thermoelectric device manufacturing method according to claim 4, wherein the slit is inserted from the open end side of the slit.

Images