WO1995031832A1 - Manufacture of thermoelectric power generation unit - Google Patents
Manufacture of thermoelectric power generation unit Download PDFInfo
- Publication number
- WO1995031832A1 WO1995031832A1 PCT/JP1995/000933 JP9500933W WO9531832A1 WO 1995031832 A1 WO1995031832 A1 WO 1995031832A1 JP 9500933 W JP9500933 W JP 9500933W WO 9531832 A1 WO9531832 A1 WO 9531832A1
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- WIPO (PCT)
- Prior art keywords
- thermoelectric
- forming
- electrode film
- photosensitive resin
- substrate
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Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/01—Manufacture or treatment
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/10—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects operating with only the Peltier or Seebeck effects
- H10N10/17—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects operating with only the Peltier or Seebeck effects characterised by the structure or configuration of the cell or thermocouple forming the device
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/0001—Technical content checked by a classifier
- H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
Definitions
- the present invention relates to a method of manufacturing a thermoelectric power generation unit in which a thermocouple in which different types of semiconductors are joined is used as a heat generating element, and several thermocouples are joined in series.
- Thermocouples generate voltage by giving a temperature difference across their ends.
- Thermoelectric power generation attempts to use this voltage as electrical energy.
- Thermoelectric generation has attracted much attention as a method that can directly convert heat energy into electric energy, and as an effective use of heat energy, including the use of waste heat.
- thermoelectric generation unit used for thermoelectric generation has a simple structure in which a plurality of thermocouples, which are thermoelectric generation elements, are joined in series, which is advantageous for miniaturization compared to other generators.
- thermocouples which are thermoelectric generation elements
- thermoelectric power generation unit has a plate-like structure as a whole, and generates heat by using a thermocouple 100 using a p-type thermoelectric material 101 and an n-type thermoelectric material 102. ⁇ A large number of elements are arranged S and they are connected in series. The hot junction 104 and the cold junction 105 of the thermocouple 100 are located on the front surface and the S surface of the plate-like thermoelectric power generation unit, and the temperature of the front and back sides Generate electricity by the difference.
- thermoelectric power generation unit that performs thermoelectric power generation is generally manufactured by the following manufacturing method.
- thermoelectric semiconductor material blocks are formed by so-called sintering, in which the alloy material is pulverized and then baked to form a block-like material.
- thermoelectric material 101 is cut by a dicing saw or the like, and divided into rectangular parallelepiped chips.
- This rectangular chip as shown in Fig. 9! ) -Type thermoelectric material 101 and n-type thermoelectric material 102 are arranged in a matrix so that they alternate.
- thermoelectric power generation unit solder welding is mainly used for this connection.
- the conventional matured power generation unit manufactured in this way has an overall size of several + cm square or more, and the logarithm of the thermocouple is about several tens of pairs.
- thermoelectric materials currently used the output voltage of thermocouples using Bi-e materials, which are said to have the best performance, is about 400 ⁇ / 3 ⁇ 4 per pair. is there.
- a portable permanent device such as a wristwatch is usually used at a temperature around room temperature
- a large temperature difference inside the portable electronic device cannot be expected.
- the temperature difference inside the wristwatch is about 2 at most.
- thermoelectric power generation unit is enlarged, but it is very difficult to consolidate 2000 pairs of thermocouples into a 1 cm square, which is about the size of a button pond. is there.
- This heat and power generation unit Size is particularly important when using it as a power source for microelectronic devices such as watches.
- thermoelectric power-generating unit in order to achieve the miniaturization of the thermoelectric power-generating unit, it suffices if the sintered body of the thermoelectric material can be finely cut and processed simply by the mechanical processing method described above.
- thermoelectric materials are often very brittle, so care must be taken not only in the cutting process but also in handling after cutting, and the production yield will naturally decline.
- thermoelectric power generation unit in the conventional manufacturing method using machining, it is considered that it is a common sense limit to handle materials with dimensions of at most about 1 mm, and the thermoelectric power generation unit was built in a size of 1 cm square Even so, the logarithm of the thermocouple, which is the thermal detector, is only about 50 pairs.
- thermocouple As a thermoelectric power generation element.
- the dance becomes so large that the current value required for the thermoelectric power generation element cannot be obtained. Therefore, after all, it is formed from the film formed by the vacuum evaporation method.
- Thermocouples are not suitable as thermoelectric probes.
- thermoelectric power generation element by this thick film method is described in, for example, Japanese Patent Application Laid-Open No. 63-70462.
- thermoelectric power generation scrap by the thick film method described in this publication, Since clean printing can be used, miniaturization is possible, and a film thickness of 10 m or more can be realized. Therefore, it is suitable for forming a thermoelectric power generation element having a lower impedance in the inner city than a thin film formed by a vacuum deposition method.
- thermoelectric material In the pretreatment process for producing the paste, there is a problem that impurities are mixed in the thermoelectric material, and a uniform solid solution cannot be formed, and the composition is distributed. Furthermore, there is a problem that cracks and the like occur during sintering.
- the pattern is formed by screen printing, it is difficult to obtain a precise power generation cut with minute dimensions with high accuracy. For these reasons, sufficient properties cannot be obtained, and the thick film method is not the optimal method for making a small thermal power generation unit.
- thermoelectric power generation unit As described above, the method of etching a film formed by the conventional machining method or the vacuum evaporation method is used to integrate a large number of thermocouples as thermoelectric elements in a minute area. It was difficult to form a thermoelectric power generation unit into a thermoelectric power generation unit, and it was not possible to produce an extremely small thermoelectric power generation unit having sufficient power.
- the present invention solves such a problem caused by the conventional method of manufacturing a thermoelectric power generation unit, and provides a thermoelectric generation unit capable of obtaining a sufficient output as a power generator and having an extremely small size with high pattern accuracy.
- the purpose is to make it easy to manufacture. Disclosure of the invention
- thermoelectric unit In order to achieve the above objectives, this effort will adopt the manufacturing methods described in the following item 1 as the manufacturing method of the thermoelectric unit.
- the manufacturing method of the first thermoelectric generation unit by this effort consists of the following steps.
- Forming a first thermoelectric structure by dissolving and removing the substrate and the electrode film.
- thermoelectric structure and the second thermoelectric structure are alternately stacked and bonded to each other, cut to a predetermined length, and then the first thermoelectric structure and the second thermoelectric structure adjacent to each other are cut.
- Cross section is replaced by wiring electrode! : A process of forming a small number of thermocouples connected in series as thermoelectric generators by joining together.
- the method of manufacturing the second mature electric power generation unit according to the present invention includes substantially the same steps as the above-described first manufacturing method, except that the first thermoelectric structure and the second thermoelectric structure are combined with each other.
- the forming step instead of the step of coating a thermosetting resin on the photosensitive resin and the first thermoelectric element or the second thermoelectric substance, the photosensitive resin and the first thermoelectric element or the second thermoelectric element are replaced.
- the step of bonding the vulnerable board to the hot body is used.
- a third method of manufacturing a heat generating power unit according to the present invention includes the following steps.
- a step of forming a composite thermoelectric structure by a step of contacting the surface on which the body is formed with an intervening insulating plate, and a step of dissolving and removing the two substrates and each electrode film.
- thermoelectric body and second thermoelectric body are connected to a wiring electrode.
- thermoelectric generation unit includes the following steps.
- thermoelectric structure the plurality of upper IS first thermostructures and the second thermoelectric structure are alternately stacked and bonded, cut to a predetermined length, and then joined to the first thermostructure and the second thermoelectric structure.
- the fifth method of manufacturing a thermoelectric unit according to the present invention comprises substantially the same steps as those of the fourth method, except that the first thermoelectric structure and the second thermoelectric structure are formed.
- the step of performing the above instead of the step of coating the thermosetting resin on the upper IE photosensitive resin and the first thermoelectric body or the second thermoelectric body, the above-described photosensitive resin and the first thermoelectric body or the second thermoelectric body or the first thermoelectric body or the second thermoelectric body are replaced.
- the step of bonding a mature insulating board on the mature body of step 2 is used.
- a sixth method for manufacturing a heat generating unit according to the present invention includes the following steps.
- a step of forming a stripe pattern using a photosensitive resin on an electrically conductive substrate different from the above-mentioned substrate, and a step of forming a stripe pattern using the above-mentioned substrate as an electrode in the opening of the photosensitive resin A step of forming a second heat sink made of a second thermoelectric material by a plating method;
- thermoelectric element Bonding the surface on which the first thermoelectric element is formed and the surface on which the second thermoelectric element is formed with a heat insulating plate therebetween; and dissolving and removing the two substrates Forming a composite thermal structure by the above steps.
- thermoelectric structures are stacked and bonded to each other, and cut into a predetermined length. Then, cross sections of the adjacent first thermoelectric body and second thermoelectric body are alternately connected by wiring electrodes. By combining them, the heat power generation cable A step of forming a plurality of thermocouples connected in series as ⁇ .
- the manufacturing method of the seventh heat and power generation unit based on this investigation includes the following steps.
- thermoelectric body made of a first thermoelectric material is formed on the first electrode film at the opening of the photosensitive resin by a plating method.
- thermoelectric body made of a second thermoelectric material on the second electrode film in the opening of the photosensitive resin using the second electrode film by a plating method
- thermosetting resin Coating a thermosetting resin on the photosensitive resin and the first and second thermoelectric elements
- a step of dissolving and removing the substrate, the first electrode film, and the second electrode film to form a matured structure is a step of dissolving and removing the substrate, the first electrode film, and the second electrode film to form a matured structure.
- thermoelectric generators a plurality of the thermoelectric structures are stacked and bonded to each other, cut to a predetermined length, and then the cross sections of the first thermoelectric body and the second mature body which are in a row are alternately connected by wiring.
- thermocouples connected in series are formed as thermoelectric generators.
- thermoelectric generator unit includes substantially the same steps as the seventh manufacturing method. Instead of the step of coating the thermosetting resin and the first and second heat bodies with the thermosetting resin, a heat insulating plate is bonded on the photosensitive resin and the first and second mature bodies. Process.
- thermoelectric generator unit is characterized in that, in the step of forming the thermoelectric structure in the seventh or eighth manufacturing method, the first step is performed by opening the photosensitive resin on the substrate.
- Thermal lightning body and second thermoelectric The steps up to the step of forming the body by the plating method are the same as those in the seventh or eighth manufacturing method.
- the step of dissolving and removing the electrode film forms a composite thermal structure.
- thermoelectric generation elements are formed.
- thermoelectric structure in the seventh manufacturing method in the step of forming a thermoelectric structure in the seventh manufacturing method, the IS-sensitive resin and the first and second thermoelectric units are formed.
- the steps up to the step of coating the thermosetting resin on the body are the same as in the seventh manufacturing method.
- thermoelectric structure as a thermoelectric generator by contacting the bodies with each other to form a thermoelectric structure.
- thermoelectric structures After a plurality of the thermoelectric structures are stacked and bonded, the ends of the adjacent mating thermocouple rows are connected to each other, and all the thermocouples are connected in series.
- the method of manufacturing the eleventh thermoelectric power generation unit according to the present invention comprises substantially the same steps as those of the tenth manufacturing method.
- the step of forming the thermoelectric structure the first 15 Instead of the step of coating the thermosetting resin on the first and second thermoelectric bodies, the step of contacting the photosensitive resin and the matured board on the first and second thermoelectric bodies is replaced by Used.
- a metal film is formed on a substrate whose surface is entirely green. 0
- the first electrode film and the second! A step of forming a striped pattern in the gap between the comb teeth of the polar film.
- a wiring electrode is formed by patterning the formed gold-extended film using an etching method, and the first thermoelectric body and the second conductor adjacent to each other are exchanged by the wiring electrode! : Forming a thermal row as a thermoelectric generator.
- thermoelectric structure is formed by the above steps.
- thermocouple rows are connected to each other, and all the thermocouples are connected in series.
- a thirteenth method of manufacturing a power supply unit according to the present invention includes the following steps.
- thermoelectric generator After bonding the first thermal structure and the second thermoelectric structure formed in each of the above steps by fitting one opening and the other non-opening of each photosensitive resin, a predetermined size is obtained.
- thermoelectric structures are stacked and bonded together via an insulating material, and the thermoelectric elements at the ends of the composite thermoelectric structure that are to be adhered to each other are wired by element end wiring, so that each thermocouple is connected in series. The process of connecting.
- the method of manufacturing the 14th thermoelectric power generation unit by Hideaki consists of the following steps.
- a photosensitive resin having an opening having a width equal to or greater than the width of the non-opening portion of the substrate and having a second stripe pattern having the same pitch as the first stripe pattern is formed on the electrode film.
- an opening of the photosensitive resin using the electrode film Forming a second thermoelectric material made of a second thermoelectric material thinner than the photosensitive resin by a plating method; and forming a second thermoelectric structure.
- thermoelectric structure and the second thermoelectric structure are bonded to each other by fitting one opening and the other non-opening of the photosensitive resin, and then cutting the photosensitive resin into a predetermined size; A step of dissolving and removing each substrate and the electrode film; and alternately wiring cross sections of the adjacent first thermoelectric element and second thermoelectric element with wiring electrodes to form a thermocouple as a thermoelectric element. Forming a composite thermoelectric structure by forming a row.
- thermocouples are connected in series by laminating a plurality of the composite thermoelectric structures via an insulating material and wiring the thermoelectric elements at the ends of the adjacent composite thermoelectric structures with element end wiring. Step of connecting to.
- the width of the opening of the first striped pattern is equal to or larger than the width of the non-opening, and the second striped pattern is formed. Should be the same as the first striped pattern.
- the photosensitive resin for forming a strip-like pattern on a substrate or an electrode film thereon may be made of an acrylic resin. It is preferable to use a photosensitive dry film or a photosensitive polyimide resin. According to such a method for manufacturing a thermoelectric power generation unit, a pattern is formed using a photosensitive resin, and a thermoelectric body is formed in the opening of the photosensitive resin by plating. Therefore, it is possible to accurately form a thermoelectric power generation element (thermocouple) having a width of the formula 1 ⁇ .
- thermoelectric element is formed by the plating method, it is possible to form a thermoelectric film having a film thickness of about 10 ⁇ m to about 1 ⁇ . It is also easy to control the thermoelectric composition by plating bath composition and voltage control.
- thermoelectric generation unit includes a photolithography process using a photosensitive resin, a plating process, a vacuum deposition and an etching process. Therefore, multiple batches can be
- thermocouple 91 By being able to form the element, the integration density of the thermocouple, which is a thermoelectric element, can be dramatically increased as compared with the conventional case. Therefore, it is possible to easily manufacture a thermoelectric power generation unit that is small but can obtain high output even with a low temperature difference.
- thermoelectric structure is formed in the openings of the photosensitive resin having the stripe-shaped pattern. For this reason, if thermoelectric structures made of different thermoelectric materials are laminated so that the non-opening and the opening (meshing portion) of the photosensitive resin are fitted together, the cross-section of the thermoelectric unit of the thermoelectric generator unit during lamination can be obtained. The amount of displacement is small.
- FIG. 1 to FIG. 8 are views for explaining a manufacturing process of a thermoelectric power generation unit according to a first embodiment of the present invention, and FIG. 1 to FIG. The figures are also used to explain the second and third embodiments, FIGS. 4 and 5 are also used to explain the second embodiment, and FIG. 8 is a diagram of the second, fourth and fifth embodiments. Also used for explanation.
- FIG. 9 is a diagram showing a part of the manufacturing process of the thermoelectric power generation unit according to the second embodiment of the present invention.
- FIGS. 10 to 13 are diagrams for explaining the manufacturing process of the thermoelectric power generation unit according to the third embodiment of the present invention.
- FIGS. 11 and 12 are diagrams of the sixth embodiment.
- FIG. 13 is also used for the description of the sixth and ninth embodiments.
- FIGS. 14 to 18 are views for explaining the manufacturing process of the thermoelectric power generation unit according to the fourth embodiment of the present invention.
- FIGS. 14 and 15 are FIGS. FIG. 17 and FIG. 18 are also used for the description of the fifth embodiment.
- FIG. 19 is a diagram showing a part of the manufacturing process of the thermoelectric power generation unit according to the fifth embodiment of the present invention.
- FIG. 20 is a view showing a part of the manufacturing process of the thermoelectric power generation unit according to the sixth embodiment of the present invention.
- FIGS. 21 to 28 are views for explaining the manufacturing process of the thermoelectric power generation unit according to the seventh embodiment of the present invention
- FIGS. 21 to 23 are FIGS.
- FIG. 25 is also used for the description of the tenth embodiment
- FIGS. 26 to 28 are also used for the description of the eighth embodiment.
- FIG. 29 is a diagram showing a part of the manufacturing process of the thermoelectric power generation unit according to the eighth embodiment and the eleventh embodiment of the present invention. '
- FIGS. 30 to 32 are views for explaining the manufacturing process of the thermoelectric power generation unit according to the ninth embodiment of the present invention, and FIG. 30 is also used to explain the 12th embodiment. I do.
- FIG. 33 and FIG. 34 are views showing a part of the manufacturing process of the thermoelectric power generation unit according to the tenth embodiment and the eleventh embodiment of the present invention.
- FIG. 35 and FIG. 36 are views showing a part of the manufacturing process of the thermoelectric power generation unit according to the 12th embodiment of the present invention.
- FIGS. 37 to 45 are diagrams for explaining a manufacturing process of the thermoelectric generator unit according to the thirteenth embodiment of the present invention.
- FIG. 46 is a perspective view showing an example of a thermoelectric power generation unit manufactured by a conventional manufacturing method.
- BEST MODE FOR CARRYING OUT THE INVENTION The method of manufacturing a thermoelectric generation unit according to the present invention will be described in more detail.
- thermoelectric power generation unit according to the first embodiment of the present invention.
- a copper plate is used for the substrate 10 shown in FIG.
- titanium (Ti) is formed as an electrode film 11 on the substrate 10 by a vacuum evaporation method.
- the thickness of this electrode film 11 is 500 nm
- the titanium film serving as the electrode film 11 also has a role of protecting the copper plate of the substrate 10 from being attacked by a plating target in a plating process described later.
- a photosensitive resin 12 is formed on the electrode film 11.
- a photosensitive dry film having a film thickness of 50 ⁇ is used, and is formed using a steel coater.
- the dry film of the photosensitive resin 12 is exposed to light using a photomask and exposed to light, and only the unexposed portion is dissolved and removed. 1 As shown in FIG. 1, a strip-like pattern is formed by photosensitive resin 12.
- the planar pattern shape of the photosensitive resin 12 after this patterning is shown by ⁇ in the plan view of FIG.
- a Teflon-based polymer film is formed on the entire back surface of the substrate 10 by using a spin coating method.
- the polymer film made of a Teflon-based material formed on the back surface of the substrate 10 has a role to prevent the formation of the plating film on the back surface of the substrate 10 in a plating process described later.
- thermoelectric body 15 made of a first thermoelectric material is formed in the opening 13 of the photosensitive resin 12 on the substrate 10 by a plating method as shown in FIG. ,
- a BiTeSe alloy which is an ⁇ -type semiconductor, is used as a material.
- a plating electrolyte for forming the first thermoelectric body 15 of the n-type semiconductor a nitric acid solution containing Bi (N 03), Te 02 and Se 2 is used.
- the electrode film 11 is used as a force source and a Pt electrode is used as the anode and a voltage of 1 V is applied between both electrodes, the BiTeSe alloy is turned into an opening in the photosensitive resin 12. It can be deposited on the two-electrode film 11 in 13.
- the first thermal element 15 can be formed only in the region on the electrode film 11 in the opening 13 of the photosensitive resin 12.
- the amount of deposition is reduced by the amount of charge calculated from the current consumption during electrolysis. Therefore, it is easy to control the first matured body 15 to a required thickness by measuring the charge amount.
- the film thickness of the first thermal element 15 is the same as that of the buttered photosensitive resin 12 as shown in FIG. 2, that is, the amount of reaction charge so that the film thickness becomes 50 ym. Set.
- composition of the alloy can be changed by changing the ionic strength of B i, T e, and S e in the plating electrolyte, and the required output voltage or
- the material of the first thermoelectric element 15 having a resistance value can be selected.
- the polymer film on the back surface of the substrate 10 is separated and removed by toluene. After that, the first thermoelectric element 15 formed on the substrate 10 is heat-treated for 1 hour in a nitrogen atmosphere at 350 ° C.
- thermosetting resins 1 6 consisting mi de resin, by forming the entire surface of the Li substrate 1 0 Supinkoti ring method, then, 1 5 0 e O and Li heat treatment C or higher, Porii Mi de resin Is cured.
- the entire substrate 10 was immersed in a nitric acid solution to dissolve all of the copper that was the material of the substrate 10, and then the titanium that was the material of the electrode film 11 was further dissolved using a 1% hydrofluoric acid solution. Dissolve (T i).
- the first thermoelectric body 15, the photosensitive resin 12 and the thermosetting resin 16 are insoluble in nitric acid and hydrofluoric acid. Therefore, as shown in FIG. 4, the first thermoelectric body 15, the photosensitive resin 12, and the thermosetting resin 16 remain as they are, and the first thermoelectric structure 20 can be formed. .
- thermoelectric structure 20 including the first thermoelectric body 15 is formed.
- the second thermoelectric structure 20 shown in FIG. Form structure 21 the difference from the above is the plating process of the thermoelectric material of the second matured body.
- the plating process of the thermoelectric material of the second thermoelectric body 17 will be described.
- thermoelectric body 17 made of a second thermoelectric material is formed in the opening 13 of the photosensitive resin 12 by a plating method. I do.
- a BiTeSb alloy which is a p-type semiconductor, is used as a material.
- thermoelectric body 17 As a plating electrolyte of the second thermoelectric body 17 which is a p-type semiconductor, a nitric acid solution containing Bi (N03), Te2 and SbC13 is used.
- a nitric acid solution containing Bi (N03), Te2 and SbC13 is used.
- the electrode film 11 is used as a force source, and a Pt electrode is used as an anode and a voltage of 1 V is applied between both electrodes, the BiTeSb alloy is converted to the photosensitive resin 1. 2 can be deposited on the electrode film 11 in the opening 13.
- the second thermoelectric element 17 is formed by the opening 1 of the photosensitive resin 12. Precipitates only in 3.
- the thickness of the second thermoelectric element 17 is controlled by the amount of reaction charge so as to be 50 ⁇ , which is the same as the thickness of the dry film.
- thermoelectric structure having a cross-sectional structure shown in FIG. 6 is obtained by cutting it to a required length.
- the surface may be polished by a rubbing method or the like.
- a gold (Au) film is formed on the entire cross section of the thermoelectric structure by a vacuum evaporation method, a sputtering method, or the like, or an electroless plating method. Further, the gold (Au) film is patterned by photolithography to form a wiring electrode 25.
- the wiring electrode 25 connects the first thermoelectric body 15 and the second thermoelectric body 17 appearing next to each other in a cross section to form a thermocouple 30. Then, by connecting all the thermocouples 30 in series, a thermoelectric generation unit can be obtained.
- the photosensitive resin 12 made of a dry film can be patterned with micron-order accuracy.
- thermoelectric body 15 and the second thermoelectric body 17 formed in the opening 13 of the photosensitive resin 12 by plating are formed of a photosensitive resin.
- Corrected form (Rule 91) It can be formed with a pattern accuracy on the order of microns, as in 12.
- thermoelectric element 15 and the second thermoelectric element 17 formed by the plating method are easy to control in thickness and control in composition, and are pre-treated just to dissolve the raw materials. Is simpler than before.
- thermocouples 30 included in the substrate 10 is 2500 pairs.
- thermoelectric generation unit When a temperature difference of 2 ° C is applied to the thermoelectric generation unit, an open-circuit voltage of 2 V is obtained, which is sufficient for driving portable electronic devices such as watches.
- thermoelectric power generation unit the length of this thermoelectric power generation unit is 2 mm
- the internal impedance is 13 k ⁇ , which is an order that can be sufficiently handled for electronic equipment.
- thermoelectric power generation unit according to the second embodiment of the present invention will be described with reference to FIGS. 1, 2, and 4 to 9.
- FIG. 1 to 8 are common to the first embodiment described above, and only FIG. 9 is added to the description of the second embodiment.
- the first step is performed up to the step of coating the polymer film, the step of forming the first thermoelectric element 15 and the second thermoelectric element 17, the step of peeling the polymer film on the back surface, and the ripening step. Same as the example.
- the second embodiment differs from the first embodiment only in that a heat insulating plate 18 is used instead of the thermosetting resin 16 as shown in FIG.
- a heat insulating plate 18 is used instead of the thermosetting resin 16 as shown in FIG.
- the heat insulating plate 18 a glass plate having a thickness of 100 ⁇ m is used.
- the photosensitive resin 12 and the first thermoelectric member 15 are bonded to each other using an epoxy-based adhesive.
- thermoelectric generation unit in which a plurality of thermocouples 30 are connected in series is obtained. Also in the method of manufacturing a thermoelectric power generation unit according to the second embodiment of the present invention, a thermoelectric power generation unit having minute dimensions can be formed with higher precision than before. Furthermore, it is easy to control the shape and composition of the thermoelectric element (thermocouple).
- thermoelectric structure 20 is interposed between the first thermoelectric structure 20 and the second thermoelectric structure 21.
- the hardness of the thermoelectric structure in the manufacturing process is increased as compared with the first embodiment, so that the reliability of the substrate 10 against distortion and warpage in the melting process is reduced.
- thermoelectric power generation unit according to the third embodiment of the present invention will be described with reference to FIGS. 1, 3, and 10 to 13.
- FIG. 1 is a diagrammatic representation of the thermoelectric power generation unit according to the third embodiment of the present invention.
- a copper plate is used for the substrate 10, a step of forming the electrode film 11 on the substrate 10, and a step of forming the photosensitive resin 12.
- the steps up to the step of removing the polymer film on the back surface of 0 and the step of heat treatment are the same as in the first embodiment.
- the substrate 10 on which the first thermoelectric element 15 is formed and the substrate 10 on which the second thermoelectric element 17 is formed are sandwiched by a heat insulating plate 18.
- a glass plate having a thickness of 10 1 ⁇ is used.
- the bonding of the substrate 10 on which the first thermoelectric element 15 is formed and the substrate 10 on which the second thermoelectric element 17 is formed is performed as shown in FIG. And the second thermoelectric body 17 are directed toward the surface of the heat insulating plate 18.
- the bonding is performed using an epoxy adhesive.
- thermoelectric structure 23 is formed.
- thermoelectric structures 23 are laminated so that the layer of the first thermoelectric body 15 and the second thermoelectric body 17 face each other, Glue with an adhesive and cut to the required length.
- each implanted thermoelectric structure 23 is separated by the remarkable epoxy adhesive used for bonding, and at this time, the first matured electric body 15 is formed. There is no conduction between the second thermoelectric element 17 and the second thermoelectric element 17.
- the surface of the scrap may be polished by using the lapping method as described above.
- a gold (Au) film is formed on the entire cross section of the element by vacuum evaporation, sputtering, or electroless plating. Then, the wiring electrode 25 is formed by patterning the gold (Au) film by photolithography.
- the wiring electrode 25 is formed by connecting the first thermoelectric body 15 and the second thermoelectric body 17 appearing next to each other in a cross section to form a thermocouple 30. Then, by connecting all the heat flute pairs 30 in series, a thermoelectric unit can be obtained.
- thermoelectric frost unit in the method of manufacturing a thermoelectric frost unit according to the third embodiment, a thermoelectric unit with a small size can be formed with higher precision than before. Furthermore, it is easy to control the shape and composition of the thermoelectric generator (thermocouple).
- the heat insulating plate 18 is made of a composite heat! Interposed between the structures 23.
- the hardness of the thermoelectric power generation unit increases, and the thermoelectric green plate 18 is halved in comparison with the second embodiment. It is suitable for further miniaturization of thermoelectric power generation unit.
- thermoelectric power generation unit As a substrate 10 ′ shown in FIG. 14, a titanium plate is used as a metal plate. Then, a photosensitive resin 12 is formed on the entire surface of the substrate 10 ′. As the photosensitive resin 1 2, a photosensitive dry film having a film thickness of 5 ⁇ Is formed using a roll coater.
- the dry film which is photosensitive resin 12
- the dry film which is photosensitive resin 12
- the image processing is used to dissolve and remove only the unexposed areas.
- the photosensitive resin 12 is formed by patterning in a stripe shape.
- a Teflon-based polymer film is formed on the back surface of the substrate 10 ′ by using a spin coating method. Coat the entire back surface.
- the polymer film formed on the back surface of the substrate 10 ′ is formed in order to prevent the formation of a mech film on the back surface of the substrate 10 ′ in a plating process described later.
- the first thermoelectric material 15 made of the first thermoelectric material is formed on the substrate 10 ′ in the opening 13 of the photosensitive resin 12 by a plating method.
- the first thermoelectric element 15 formed in the opening 13 of the photosensitive resin 12 uses a BiTeSe alloy, which is an n-type semiconductor, as a material.
- thermoelectric element 15 As the plating electrolyte of the first thermoelectric element 15 which is an ⁇ -type semiconductor, a nitric acid solution containing ⁇ i (N 03), Te 02 and Se 02 is used, and When the substrate 10 ′ is used as a force source, a Pt electrode is used as the anode, and a voltage of 1 V is applied between both electrodes of the force source node.
- the alloy can be deposited on the substrate 10 in the opening of the photosensitive resin 12.
- the back surface of the substrate 10 ′ is protected by the polymer film as described above. For this reason, the first thermoelectric body 15 can be deposited only in the opening of the photosensitive resin 12.
- the amount of deposition is determined by the amount of electric charge calculated from the current consumption during electrolysis, so that the first thermoelectric element 15 is required by measuring the amount of electric charge. It is easy to control the thickness
- the film thickness of the first thermoelectric element 15 is set to be the same as that of the photosensitive resin 12, that is, 50 ⁇ .
- composition of the alloy of the first thermoelectric element I5 can be changed by changing the ion concentration of B i, D e and S e in the electrolytic solution. By setting these ion concentration conditions, a material having a required output voltage or a required resistance value can be selected as the first thermoelectric element 15.
- the polymer film used as the plating protection film on the lining surface of the substrate 10 ' is peeled off and removed with toluene.
- substrate 1. Heat-treat the first thermoelectric element 15 formed thereon in a nitrogen atmosphere at a temperature of 350 for 1 hour.
- the heat treatment in the nitrogen atmosphere is performed in order to equalize the alloy composition of the first thermoelectric body 15 and to improve the output of the thermoelectric generation unit.
- thermosetting resin 16 made of a polyimide resin is formed on the photosensitive resin 12 of the substrate 10 and the upper surface of the first thermoelectric element 15.
- This thermosetting resin 16 is formed by a spin coating method.
- thermoelectric generator having the thermosetting resin 16 formed on the upper surface of the photosensitive resin 12 and the first thermoelectric element 15 was immersed in a 1% hydrofluoric acid solution. Dissolve and remove titanium, which is the material of the substrate 10,
- the first thermoelectric body 15, the photosensitive resin 12 and the thermosetting resin 16 remain as they are because they are insoluble in hydrofluoric acid, and the first thermoelectric structure 20. Can be formed.
- thermoelectric structure 20 in which the first thermoelectric body 15 is formed, and the same steps as shown in FIG. 5 are performed in the first embodiment. Form the same second thermoelectric structure 2 1 can do.
- the difference from the above is the plating process of the second thermoelectric element 17 made of the second thermoelectric material.
- the plating process of the second thermal element 17 made of the second thermoelectric material will be described.
- thermoelectric material is formed on the substrate 10 ′ of the opening 13 of the photosensitive resin 12 by a plating method.
- thermoelectric element 17 a BiTeSb alloy which is a p-type semiconductor is used as a material.
- thermoelectric body 17 As a plating electrolyte of the second thermoelectric body 17 which is a p-type semiconductor, a nitric acid solution containing Bi (N03), Te2 and SbC13 is used.
- a Pt electrode is used as the anode, and a voltage of 1 V is applied between the anode force electrodes, the BiTeSb alloy is exposed.
- thermoelectric element 17 is deposited only in the opening 13 of the photosensitive resin 12 because the back surface of the substrate 10 ′ is protected by the polymer film.
- the thickness of the second thermal element 17 is controlled by a reaction charge cell so as to be 50 ⁇ , which is the same as that of the dry film as the photosensitive resin 12.
- the composition of the alloy is changed by changing the ion concentration of B i, Te and S b in the plating electrolyte of the body 17, and the second thermoelectric body 17 has the required output voltage or resistance value Control
- thermoelectric structure 21 is formed according to the same processing method as the manufacturing process of the first thermoelectric structure 20 described above.
- the first matured structure 20 and the second thermoelectric structure 21 are alternately stacked on top of each other, and an epoxy-based adhesive is used. Adhere both.
- thermosetting structure in which a thermosetting resin 16 is interposed between the first thermoelectric structure 20 and the second thermoelectric structure 21 is formed.
- Body can be formed.
- a gold (Au) film is formed on the entire cross-section by a vacuum deposition method, a sputtering method, or an electroless plating method.
- the gold (Au) film is patterned by photolithography to form wiring electrodes 25 in the same manner as in the first embodiment shown in FIG.
- This wiring electrode 25 connects the first thermoelectric element 15 and the second thermoelectric element 17 that appear next to each other in the cross section to form a mature couple 30.
- thermocouples 30 By connecting all the thermocouples 30 in series, a power generation unit can be obtained.
- thermoelectric generator thermocouple
- thermoelectric power generation unit in the fourth embodiment, as compared with the first to third embodiments of the present invention, a titanium film serving as a groove 11 is not formed on a substrate 10 ′. From this, according to the method of manufacturing a thermoelectric power generation unit in the fourth embodiment, there is an effect that the manufacturing process is further simplified.
- the first As shown in Fig. 4 and Fig. 15, a titanium plate is used for the substrate 10 ', the coating and patterning processes of the photosensitive resin 12 are performed, and the coating of the polymer film on the back surface of the substrate 10' is performed.
- the steps up to the step of forming the first thermoelectric element 15 or the second thermoelectric element 17, the step of removing the polymer film on the back surface, and the heat treatment step are the same as those of the fourth embodiment.
- a heat insulating plate 18 is attached to the photosensitive resin 12 of the substrate 10 ′ and the first resin. Formed on generator 15.
- a glass plate having a thickness of ⁇ ⁇ ⁇ ⁇ ⁇ is used, and is bonded to the upper surfaces of the photosensitive resin 12 and the first power generator 15 by an adhesive means.
- thermoelectric structure 20 titanium as a material of the substrate 10 ′ is dissolved and removed using a 1% hydrofluoric acid solution to form a first thermoelectric structure 20.
- second thermoelectric structure 21 titanium as a material of the substrate 10 ′ is dissolved and removed using a 1% hydrofluoric acid solution to form a first thermoelectric structure 20.
- first thermoelectric structure 20 and the second thermoelectric structure 21 are connected to each other by a heat insulating plate 1. 8 can be glued to the eyebrows and cut to form a thermoelectric structure,
- a gold (An) film is formed on the entire cross section by a vacuum deposition method, a sputtering method, or an electroless plating method. Thereafter, the gold (Au) film is patterned by photolithography to form a rooting electrode 25 in the same manner as in the first embodiment shown in FIG. Get.
- thermoelectric power generation unit having a small size can be formed with higher accuracy than before. Further, the shape and the shape of the thermoelectric power generation unit (thermocouple) can be improved. The composition can be easily controlled.
- thermoelectric power generation unit according to the sixth embodiment of the present invention will be described with reference to FIGS. 14, 15 and 20, and FIGS. 11 to 13. .
- thermoelectric power generation unit in the method for manufacturing a thermoelectric power generation unit according to the sixth embodiment of the present invention, as shown in FIGS. 14 to 16, a titanium plate is used for the substrate 10 ′ and the photosensitive resin 1 is used.
- the substrate on which the first matured body 15 is formed and the second The substrate on which the thermoelectric body 17 is formed is bonded via the heat insulating plate 18.
- the heat insulating plate 18 As the heat insulating plate 18, a glass plate having a thickness of ⁇ ⁇ ⁇ is applied.
- the substrate 10 'on which the first thermoelectric body 15 is formed and the substrate 10' on which the second 'thermoelectric body 17 is formed are bonded to the first thermoelectric body 15 and the second The surface on which the thermoelectric body 17 is formed is directed to the heat-insulating plate 18 side, and an epoxy-based adhesive is used.
- thermoelectric structure 23 shown in FIG. 11 as in the third embodiment.
- thermoelectric structures 23 are laminated so that the first thermoelectric body 15 and the second thermoelectric body 17 face each other, and an epoxy-based adhesive is Glue them together and cut them to the required length.
- thermoelectric body 15 is formed. Between the second thermoelectric element 17
- the element surface may be polished by the rubbing method as described above.
- a gold (Au) film is formed on the entire cross section of the element by a vacuum evaporation method, a sputtering method, or an electroless plating method. Further, the gold (Au) film is patterned by photolithography to form a wiring electrode 25.
- the wiring electrode 25 connects the first thermoelectric body 15 and the second thermoelectric body 17 appearing next to each other in a cross section to form a thermocouple 30.
- thermoelectric generation unit By connecting all the thermocouples 30 in series, a thermoelectric generation unit can be obtained.
- thermoelectric power generation unit In the method of manufacturing a thermoelectric power generation unit according to the sixth embodiment, a micro-sized power generation unit having a small size can be formed with higher precision than before, and the shape and the shape of the power generation element (thermocouple) can be improved.
- the group is easy to control ⁇
- thermoelectrically luminescent plate 18 is interposed between the composite thermoelectric structures 23. From this fact, it is possible to develop the system! ; As the hardness of the unit increases, the thickness of the thermoelectric power generation element on which the thermoelectric power generation element is stacked is thinner because only half of the thermoelectrically green plate 18 is required as compared with the fifth embodiment. Suitable for miniaturization.
- thermoelectric power generation unit according to the seventh embodiment of the present invention will be described with reference to FIGS. 2IS to 28.
- a copper plate whose front surface is covered with an absolutely green film (not shown) such as a SiO 2 film is used.
- Zemmidorimaku consisting S i 0 2 has two electrode films to be formed in the process steps after this are coatings having a function of preventing a short circuit by copper of the substrate 1 0 beta
- a titanium film is formed as an electrode film on the entire front surface of the substrate 10.
- This electrode film is formed to a thickness of 500 nm by a vacuum evaporation method.
- the titanium film which is the electrode film
- the titanium film is patterned using photolithography technology and etching technology so that the two-dimensional pattern shape of the electrode film becomes a comb-tooth shape that enters each other.
- a first electrode film 31 and a second electrode film 32 are formed.
- the plan pattern shape of the first electrode film 31 and the second electrode film 32 is shown in the plan view of FIG. 22.
- the first electrode film 31 and the second electrode film 32 are shown.
- the photosensitive resin 12 is formed on the entire surface of the substrate 10 on which is formed.
- a photosensitive dry film having a thickness of 5 O z m is formed using a roll coater.
- a strip-like shape is formed in the gap region where the first electrode film 31 and the second electrode film 32 are not formed by using the photolithography technique.
- the photosensitive resin 12 is formed in a shape that is patterned in
- a Teflon-based polymer film is coated on the entire back surface of the substrate 10 by using a spin coating method. deep.
- the first electrode film 31 in the opening 13 of the photosensitive resin 12 is formed on the first electrode film 31 by using a plating method. 1 heat! Form body 15;
- thermoelectric element 15 formed on the first electrode film 31 an Bi-type e-Se alloy which is an n-type semiconductor is used as a material.
- thermoelectric body 15 As a plating electrolyte for the first thermoelectric body 15 which is a type II semiconductor, a nitric acid solution containing Bi (N 03), Te 02 and Se 02 is used.
- a Pt electrode is used as the anode, and an IV voltage is applied between the force node electrodes, the BiTeSe alloy is formed.
- the thickness of the first thermoelectric body 15 is controlled by the reaction load, and The thickness of the first thermoelectric body 1 ⁇ is set so as to be 50 ⁇ m, which is almost the same as the thickness of the optical resin 12.
- a second matured body 17 made of a second thermoelectric material is formed on the second electrode film 32 in the opening of the photosensitive resin 12 by using a plating method.
- thermoelectric body 17 made of the second thermoelectric material formed on the second electrode film 32 a BiTeSb alloy which is a ⁇ -type semiconductor is used as a material.
- the second thermoelectric body 17 which is a p-type semiconductor
- a nitric acid solution containing Bi (N03), Te2 and SbC13 is used as a plating electrolyte of the second thermoelectric body 17 which is a p-type semiconductor.
- a Pt electrode is used as the anode, and a voltage of 1 V is applied between the cathode electrodes, the BiTeSb alloy is formed. It is deposited on the second electrode film 32 in the opening of the photosensitive resin 12.
- the thickness of the second thermoelectric layer 7 formed on the second electrode film 32 is controlled by the amount of reaction charge so as to be 50 ⁇ m, which is the same as that of the dry film as the photosensitive resin 12. I do.
- thermoelectric body 15 and the second thermoelectric body 17 After the two plating processes of the first thermoelectric body 15 and the second thermoelectric body 17, the polymer film on the back surface of the substrate 10 is peeled off and removed with toluene. Then, the first thermoelectric body 15 and the second thermoelectric body 17 are subjected to a heat treatment for 1 hour in a nitrogen atmosphere at a temperature of 350 ° C.
- thermosetting resin 16 made of polyimide resin was placed on the upper surfaces of the first thermoelectric body 15, the second thermoelectric body 17 and the photosensitive resin 12. Form.
- the thermosetting resin 16 is formed by a spin coating method.
- thermoelectric structure having the mature hardening resin 16 formed on the upper surfaces of the second mature body 15, the second thermoelectric body 17, and the photosensitive resin 12 is immersed in a nitric acid solution. All of the copper of the material of the substrate 10 is dissolved. Then 1
- Revised paper (Rule 91) By dipping in a hydrofluoric acid solution, the SiO 2 film as the insulating film and the titanium film as the first electrode film 31 and the second electrode film 32 are dissolved and removed.
- thermoelectric structure 24 as shown in FIG. 26 can be formed.
- thermoelectric structures 24 are laminated and bonded using an epoxy adhesive. Then, by cutting to a required length, a thermoelectric structure in which a plurality of thermoelectric structures 2 are stacked as shown in FIG. 27 is obtained.
- the element surface may be polished by the lapping method or the like as described above.
- a gold (Au) film is formed on the entire cross-section of the thermoelectric structure that has been scrapped by a vacuum evaporation method, a sputtering method, or an electroless plating method.
- a gold (Au) film is patterned by photolithography to form a wiring pole 25.
- thermoelectric power generation unit can be formed by connecting the thermocouples 30 in series.
- thermoelectric body 15 and the second thermoelectric body 17 connected in the same thermoelectric structure 24 are connected to form a hot compress pair 30.
- a thermocouple 30 may be formed between the adjacent thermoelectric structures 24.
- thermocouples thermocouples
- thermoelectric power generation unit according to the eighth embodiment of the present invention will be described with reference to FIGS. 21 to 24 and FIGS. 26 to 29.
- a copper plate covered with an insulating film made of Si02 is used for the substrate 10, and the electrode film is used.
- the film coating step, the step of forming the first thermoelectric element 15 and the second thermoelectric element 17, the step of peeling the polymer film on the back surface, and the heat treatment step are the same as in the seventh embodiment. is there.
- thermosetting resin 16 is used instead of the thermosetting resin 16 as shown in FIG.
- a glass plate having a thickness of 100 ⁇ m was used as the heat insulating plate 18 using an epoxy-based adhesive, and the first thermoelectric member 15, the second matured member 17 and the photosensitive resin were used. Adhere to the top surface with 1 2.
- thermoelectric structure 24 (a heat insulating plate 18 is used in place of the thermosetting resin 16) as shown in FIG. 26.
- thermoelectric structures 24 are laminated, bonded and cut, and a wiring electrode 25 is formed on a cross section to form a thermoelectric generator unit. Get a bird.
- thermoelectric power generation unit having a small size can be formed with higher precision than before. Furthermore, it is easy to control the shape and composition of thermoelectric generators (thermocouples).
- thermoelectric power generation element of the eighth embodiment According to the method of manufacturing the thermoelectric power generation element of the eighth embodiment,
- thermoelectric structures 24 Since the heat insulating plate 18 is interposed between the thermoelectric structures 24, it is possible to cope with a large-sized substrate.
- thermoelectric power generation unit according to the ninth embodiment of the present invention will be described with reference to FIGS. 22 to 25 and FIGS. 30 to 32.
- a copper plate covered with a SiO 2 film is used as an insulating film on a substrate 10.
- the steps up to the step of forming the first thermoelectric element 15 and the second thermoelectric element 17, the step of removing the polymer film on the back surface, and the heat treatment step are the same as those of the seventh embodiment.
- thermoelectric elements 1.5 and the second thermoelectric elements 17 are formed are attached with a heat insulating plate 18 interposed therebetween.
- a heat insulating plate 18 As the heat insulating plate 18, a glass plate having a thickness of 100 / Xm is used.
- the bonding process of the two substrates on which the first thermoelectric body 15 and the second thermoelectric body 17 are formed is performed on the surface side on which the first thermoelectric body 15 and the second thermoelectric body 17 are formed.
- thermoelectric body 15 and a second thermoelectric body 17 are formed, and the two substrates joined together with a heat insulating plate 18 interposed therebetween. Is immersed in a nitric acid solution to dissolve and remove the copper of the material of the substrate 10, and then immersed in a 1% hydrofluoric acid solution to form an insulating film made of SiO 2, the first electrode film 31 The titanium which is the electrode film 32 is dissolved to form a complex matured structure 26.
- thermoelectric structures 26 are laminated, and each is bonded to each other using an epoxy-based adhesive, and cut to a required length.
- thermoelectric structures 26 are separated by the insulating epoxy adhesive used for bonding. At this time, the first thermoelectric body 15 There is no continuity between and the second thermoelectric element 17.
- the element surface may be polished by using a lapping method or the like as described above.
- a gold (Au) film is formed on the entire cross section of the element by a vacuum evaporation method, a sputtering method, or an electroless plating method. Further, the gold (Au) film is patterned by one photolithography technique to form the wiring electrode 25.
- the wiring electrode 25 connects the first thermoelectric body 15 and the second thermoelectric body 17 appearing next to each other in a cross section to form a thermocouple 30.
- thermoelectric generation unit By connecting all the thermocouples 30 in series, a thermoelectric generation unit can be obtained.
- thermoelectric power generation unit having a minute dimension can be formed with higher precision than before. Further, it is easy to control the shape and composition of the thermoelectric power generation element.
- the heat insulating plate 18 is interposed between the composite thermoelectric structures 26. This increases the hardness of the thermoelectric power generation unit, and requires only half the heat insulating plate 18 as compared with the eighth embodiment. Therefore, the thickness of the laminated thermoelectric power generation unit is small. It is suitable for further miniaturization.
- thermoelectric generation unit according to the tenth embodiment of the present invention will be described with reference to FIGS. 21 to 25, FIGS. 33 and 34.
- a substrate 10 made of a copper plate covered with an insulating film made of a SiO 2 film is used on the front surface of the substrate 10.
- the insulating film made of S i ⁇ 2 is a film having a role of preventing a short circuit between the two electrode films formed in the subsequent process due to copper on the substrate 10.
- the first electrode film 31 and the second electrode film 32 are formed on the front surface of the substrate 10 with a titanium film.
- This titanium film is formed to a thickness of 500 nm by a vacuum deposition method.
- this titanium film is patterned using photolithography technology and etching technology so that the planar shape becomes two interdigitated comb-teeth shapes, and the first electrode film 31 and the second electrode film 31 are patterned.
- An electrode film 32 is formed.
- the planar pattern shapes of the first electrode film 31 and the second electrode film 32 are as shown in the plan view of FIG.
- the first electrode film 31 and the second electrode film 32 are formed in a comb-like pattern that forms a gap between each other.
- a photosensitive resin 12 is formed on the entire surface of the substrate 10 on which the first electrode film 31 and the second electrode film 32 'have been formed.
- a photosensitive dry film having a thickness of 5 ⁇ is formed using a roll coater.
- the photosensitive resin 12 is striped in the gap region between the first electrode film 31 and the second electrode film 32 as shown in FIG. Is patterned.
- a Teflon-based polymer film is formed on the back surface of the substrate 10 by spin coating on the back surface of the substrate 10. To be coated.
- thermoelectric material made of the first thermoelectric material is first applied on the first electrode film 31 in the opening of the photosensitive resin 12 by using a plating method.
- thermoelectric element 15 formed on the first electrode film 31 a BiTeSe alloy which is an ⁇ -type semiconductor is used as a material.
- a nitric acid solution containing B i (N 03), T e ⁇ 2, and S e ⁇ 2 is used.
- a Pt electrode is used as the anode, and a voltage of 1 V is applied between the force source and the anode electrode.
- eSe alloy is deposited on the first electrode film 31 in the opening of the photosensitive resin 12.
- the thickness of the first thermoelectric element 15 is controlled according to the amount of reaction charge so that the thickness of the first thermoelectric element 15 is 50 ⁇ m, which is almost the same as that of the photosensitive resin 12. Set the film thickness of 5.
- thermoelectric body 17 made of a second thermoelectric material is formed on the second electrode film 32 by using a plating method.
- thermoelectric body 17 As a plating electrolyte for forming the second thermoelectric body 17 which is a p-type semiconductor, a nitric acid solution containing Bi (N03), Te2 and SbC13 is used.
- a nitric acid solution containing Bi (N03), Te2 and SbC13 is used as a plating electrolyte for forming the second thermoelectric body 17 which is a p-type semiconductor.
- the thickness of the second electrode film 32 is controlled by the amount of reaction charge so as to be 50 ⁇ m, which is the same as that of the photosensitive resin 12.
- thermoelectric body 15 and the second thermoelectric body 17 After two plating processes of the first thermoelectric body 15 and the second thermoelectric body 17, the polymer film on the back surface of the substrate 10 is peeled and removed with toluene. Then, the first thermoelectric element 15 and the second thermoelectric element 17 are subjected to a heat treatment for 1 hour in a nitrogen atmosphere at a temperature of 350 ° C.
- thermosetting resin 16 made of a polyimide resin is placed on top of the photosensitive resin 12, the first thermoelectric body 15, and the second thermoelectric body 17. Then, it is formed by a spin coating method.
- thermoelectric structure was immersed in a nitric acid solution, and the substrate 10
- thermoelectric body 15 When the substrate 10 is dissolved, the first thermoelectric body 15, the second thermoelectric body 17, the photosensitive resin 12, and the thermosetting resin 16 remain as they are because they are insoluble in nitric acid.
- first electrode film 31 and second electrode film 32 made of the remaining insulating film made of SiO 2 and titanium film were dissolved and removed using hydrofluoric acid, and FIG. As shown in (1), the starting surface 33 of the first thermoelectric element 15 and the second thermoelectric element 17 is made to appear.
- thermoelectric structure 27 having a large number of thermocouples 30 ′ can be formed.
- thermoelectric structures 27 are laminated and bonded using an epoxy adhesive.
- thermoelectric generation unit By connecting all the thermocouples 30 'in series, a thermoelectric generation unit can be formed.
- thermoelectric power generation unit having a minute dimension can be formed with higher precision than before. Furthermore, it is easy to control the shape and composition of the thermoelectric element (thermocouple).
- thermoelectric power generation unit according to the eleventh embodiment of the present invention will be described with reference to FIGS. 33 and 34 and the like.
- a copper plate covered with an insulating film made of Si02 is used for the substrate 10 to form an electrode film made of titanium. And the first electrode film 31 and the second electrode film 32, and the photosensitive resin 12 coating process.
- Corrected form (Rule 91) A turning step, a step of coating a polymer film on the back surface of the substrate 10, a step of forming the first thermoelectric element 15 and the second thermoelectric element 17, and a step of peeling the polymer film on the back surface
- the heat treatment step is the same as in the tenth embodiment described above.
- thermosetting resin 16 a heat insulating plate 18 made of glass as shown in FIG. 29 is used instead of the thermosetting resin 16.
- the thickness of the heat insulating plate 18 is 1 ⁇ 1 ⁇ , and the upper surface of the first thermoelectric body 15, the second thermoelectric body 17 and the photosensitive resin 12 is used. Is bonded using an epoxy adhesive.
- the copper of the material of the substrate 10 is dissolved with nitric acid, and the SiO 2 film as the insulating film and the titanium as the first electrode film 31 and the second electrode film 32 are further reduced to 1% fluorine. Dissolve and remove using an acid solution. Thereafter, as shown in FIG. 33, a wiring electrode 35 is formed on the plating start surface 33 by using gold (Au), and a thermoelectric structure 27 is formed.
- thermoelectric generation unit is obtained by connecting all thermocouples in series.
- thermoelectric power generation device having a minute dimension can be formed with higher precision than before. Furthermore, it is easy to control the shape and composition of the thermoelectric generator. Further, since the heat insulating plate 18 is interposed between the plurality of thermoelectric structures 27, it is possible to cope with a large-sized substrate.
- thermoelectric power generation unit according to the 12th embodiment of the present invention will be described with reference to FIGS. 35 and 36.
- a copper plate covered with a SiO 2 film as an insulating film was used for a substrate 10 to form an electrode film made of titanium. Forming and patterning the first electrode film 31 and the second electrode film 32, and coating the photosensitive resin 12;
- Corrected form (Rule 91) A patterning step, a coating step of a polymer film on the back surface of the substrate 10, a step of forming the first thermoelectric body 15 and the second thermoelectric body 17, and a step of forming a height of the back surface of the substrate 10.
- the steps up to the peeling step of the molecular film and the heat treatment step are the same as those of the tenth embodiment described above.
- thermoelectric body 15 and the second thermoelectric body 17 are formed are stuck and sandwiched by a heat insulating plate 18.
- a heat insulating plate 18 As the heat insulating plate 18, a glass plate having a thickness of 1 ⁇ ⁇ is used.
- thermoelectric element 15 and the second thermoelectric element 17 are bonded together.
- the surface is formed so as to face the heat-insulating plate 18 side, and an epoxy-based adhesive is used.
- the entire element bonded to the first thermoelectric element 15 and the second thermoelectric element 17 via the heat insulating plate 18 was immersed in a nitric acid solution.
- the copper of the material of the substrate 10 is dissolved and removed, and then immersed in a 1% hydrofluoric acid solution to form an insulating film made of SiO 2 and a first electrode film 31 made of titanium and a second electrode film 3 made of titanium 2 Dissolve and remove.
- thermoelectric structure 28 can be formed by the above processing steps.
- thermoelectric structure 28 is laminated, and each composite thermoelectric structure 28 is bonded using an epoxy adhesive.
- the composite thermoelectric structure 28 is separated by an insulating epoxy-based adhesive used for bonding, and the conduction between the first thermoelectric body 15 and the second thermoelectric body 17 is established. It has not been removed.
- thermoelectric power generation unit can be obtained.
- thermoelectric power generation unit having minute dimensions can be formed with higher accuracy than before. Further, it is easy to control the shape and composition of the thermoelectric generation element.t Further, since the heat insulating plate 18 is interposed between the composite thermoelectric structures 28, the hardness of the thermoelectric generation unit increases, Since only one half of the glass plate is required as compared with the embodiment, the thickness of the thermocouple to be laminated becomes thin, which is suitable for further miniaturizing the thermoelectric power generation unit.
- the substrate 10 is made of a thermoelectric material, a dry film, or a polyimide instead of a copper plate or a titanium plate. A material that does not attack the metal and can be dissolved by etching may be used.
- the substrate 10 As a material of the substrate 10, as long as it is a metal material, an iron plate, a nickel plate, a zinc plate, an aluminum plate, a brass plate, or the like can be applied as a material, and further, a ceramic such as a glass plate or alumina can be used. It can be used as substrate 10.
- the embodiment has been described in which a titanium film is applied as the electrode film 11, the first electrode film 31, and the second electrode film 32 formed on the substrate 10.
- the titanium film used as the electrode film 11, the first electrode film 31, and the second electrode film 32 may be made of another metal film as long as the material does not dissolve in the plating solution. It is also possible to change to a material.
- a gold (Au) film, a platinum film, a Pd film, a Ta film, or the like can be applied as a substitute for the titanium film.
- the wiring electrode 25 not only a gold (Au) film but also other metal film materials such as a Cu film, an A1 film, a Ni film, and a Fe film can be applied.
- patterning is performed by forming a film, photolithography and etching.
- J Corrected paper (Rule 91 )
- portions other than those requiring electrode formation are covered with a predetermined mask material, a metal film material is formed on the entire surface by vapor deposition, and then the metal mask is removed to remove the electrode pattern.
- a so-called mask vapor deposition method for forming can also be used.
- a printing method a forming method of attaching a patterned electrode on the surface of another plate-like material, or the like can be used.
- a photosensitive dry film is used as the photosensitive resin 12 when the material of the first thermoelectric body 15 and the second thermoelectric body 17 is subjected to the plating process.
- a photosensitive polyimide can be used as the photosensitive resin.
- the thickness of the first thermoelectric body 1 ⁇ and the second thermoelectric body 17 is about 10 ⁇ m, a rubber-based photoresist or a cinnamic acid-based photoresist can be used. It can be used as a photosensitive resin when the thermoelectric material is subjected to a sticking process.
- thermosetting resin 16 an epoxy-based adhesive resin such as a acrylic resin may be used as the thermosetting resin. Can be used.
- thermosetting resin 16 can be formed not only by a spin coating method but also by a spray coating method, a roll coating method, or a process such as applying a film. .
- the heat insulating plate 18 is a thin plate that has poor heat conductivity and is not easily deformed, such as a hard plastic plate, the heat insulating plate is used. Applicable as 18.
- thermoelectric material uses a BiTeSe alloy for an n-type semiconductor and a BiTeSeb alloy for a p-type semiconductor.Either force of Se or Sb is not mixed.
- An n-type semiconductor and a p-type semiconductor can also be produced by the difference in the concentration ratio between Bi and Te.
- thermoelectric material using a substance other than the above can be used as the first thermoelectric body 15 and the second thermoelectric body 17.
- thermoelectric power generation unit according to the thirteenth embodiment of the present invention will be described with reference to FIGS. 37 to 45.
- a copper plate was used for the substrate 1, and titanium (T i) was formed on the entire surface of the substrate 10 by a vacuum evaporation method with a film thickness of 500 ⁇ ⁇ . Then, an electrode film 11 is formed.
- the electrode film 11 made of the titanium film has a function of protecting the copper plate, which is the substrate 10, from being damaged by the plating solution in a step described later.
- a photosensitive dry film having a film thickness of 50 m was formed in two layers using a roll coater on the electrode film 10 as the photosensitive resin 12, and the total film thickness of the photosensitive resin 12 was reduced. ⁇ ⁇ ⁇ ⁇ ⁇ .
- the photosensitive resin I 2 consisting of a dry film is exposed to light using a photomask to expose it, and photolithography technology, which is a so-called exposure and development process of dissolving and removing only the unexposed portions, is used.
- the photosensitive resin 12a having the first striped pattern is formed by patterning in a striped shape as shown in FIG.
- the photosensitive resin 12a having the first strip pattern has openings on the surface of the electrode film 11, that is, a portion to be subjected to dissolution processing by photolithography technology and a non-opening portion not subjected to dissolution processing. Form.
- the shape of the first striped pattern is set such that the width Wa of the opening of the photosensitive resin 12a is wider than the width Wb of the non-opening as shown in FIG. 44.
- the width W a of the portion is 150 ⁇ m and the width W b of the non-opening portion is 50 ⁇ .
- a Teflon-based polymer film 19 is spin-coated on the back surface of the substrate 10 as shown in FIG.
- the Teflon-based polymer film 19 on the rear surface of the substrate 10 is formed on the entire surface by a single-pinning method.
- thermoelectric element 15 As the first thermoelectric element 15, a BiTeSe alloy, which is an n-type semiconductor, is used as its material.
- a nitric acid solution containing Bi (N 03), Te 02 and Se 02 is used as the plating electrolyte.
- the electrode film 11 is used as a force source and a platinum (Pt) electrode is applied to the anode and a voltage of about 1 V is applied between the electrodes, the first thermoelectric element made of a BiTeSe alloy is applied.
- the body 15 is deposited on the electrode film 11 in the opening 13a of the photosensitive resin 12a.
- thermoelectric body 15 is deposited only in the opening 13a of the photosensitive resin 12a.
- the amount of deposition is determined by the amount of charge calculated from the current consumption during electrolysis. For this reason, it is easy to control the first thermoelectric body 15 to a predetermined thickness by measuring the charge amount.
- the film thickness of the first thermoelectric body 15 is set to be half the film thickness of the photosensitive resin 12a previously patterned, that is, 50 ⁇ m.
- thermoelectric structure 41 shown in FIG. 39 is formed.
- thermoelectric structure 42 shown in FIG. 40 can be formed by performing substantially the same processing steps as in the method of manufacturing the first thermoelectric structure 41 described above.
- thermoelectric structure 42 is different from the method of forming the first thermoelectric structure 1.
- the method of forming the second thermoelectric structure 42 is the same as the method of forming the first thermoelectric structure 41 until the formation of a photosensitive resin or a polymer film having a striped pattern.
- the processing steps are the same as those described with reference to FIG. 3, FIG. 38 and FIG.
- the patterning shape of the photosensitive resin 12b used to form the second thermoelectric structure 42 is used in the method of forming the first thermoelectric structure 41. It is formed so as to have the same opening width W a, non-opening width W b, and thickness as the first striped pattern 12 a shown in FIGS. 38 and 44. .
- thermoelectric structure 41 and the second Elements required for the formation of the thermoelectric structure 42 can be made common. As a result, the efficiency in manufacturing the thermoelectric power generation unit can be improved.
- thermoelectric structure is formed as described later. Since the body 41 and the second thermoelectric structure 42 can be correctly fitted in shape, the production efficiency of the thermoelectric power generation unit can be increased without hindering the following steps.
- the method of forming the second thermoelectric structure 42 differs from the method of forming the first matured electric structure 41 described above in the process of plating the thermoelectric material of the second thermoelectric body 17. .
- the plating process of the second thermoelectric body 17 will be described.
- thermoelectric body 17 made of the second matured material is formed.
- a BiTeSb alloy which is a p-type semiconductor, is used.
- the back surface of the substrate 10 is protected by the polymer film 19, so that the second thermoelectric element 17 is deposited only in the opening 13b of the photosensitive resin 12b. I do.
- the thickness of the second thermoelectric element 17 is controlled by the amount of reaction charge so that the thickness is 5 ⁇ , which is half the thickness of the photosensitive resin 12 b.
- Te and Sb By changing the ion concentration of Te and Sb.
- the composition of the alloy of the second thermoelectric element 17 can be changed, and control is performed so as to have a required output voltage or resistance value by setting these conditions. .
- the second thermoelectric structure 42 in which the second thermoelectric body 17 is formed on the substrate 10 can be formed.
- thermoelectric structure 41 and the second thermoelectric structure 42 are formed in pairs, and the surfaces on which the photosensitive resins 12a and 12b are formed are formed. Are bonded to each other using a bonding agent 43 made of an epoxy-based adhesive so that they face each other.
- the non-opening portion of the photosensitive resin 12 a on the first thermoelectric structure 41 1 is subjected to an adhesive treatment so as to be fitted to a position above the second thermoelectric body 17.
- thermoelectric element 15 and the second thermoelectric element 17 have a structure in which the relative positional relationship falls within a certain interval, and the subsequent wiring steps for the thermoelectric element are facilitated.
- thermoelectric body 15 and the second thermoelectric body 17 do not come into contact with each other. , 17 are electrically insulated.
- thermoelectric power generation element This heat treatment in a nitrogen atmosphere is for the purpose of homogenizing the alloy composition of the first thermoelectric element 15 and the second thermoelectric element 17, which leads to an improvement in the output of the thermoelectric power generation element.
- the heat treatment in the nitrogen atmosphere here is at a high temperature, but if the photosensitive resin 12 is exposed to a sufficient amount of light during the patterning treatment of the photosensitive resin 12 shown in FIG.
- the deformation such as heat shrinkage that occurs in the photosensitive resins 12a and 12b after patterning is slight, and does not pose a practical problem.
- thermoelectric structure 42 the element in which the first mature electric structure 41 and the second thermoelectric structure 42 are integrated is cut into a required size.
- the lapping may be affected.
- the surface may be polished using a method or the like.
- the entire element is immersed in a nitric acid solution to dissolve all the copper on the substrate 10, and then the titanium as the electrode film 11 is dissolved and removed using a hydrofluoric acid solution.
- thermoelectric element 15 and the second thermoelectric element 17 are insoluble in nitric acid and hydrofluoric acid, and thus are left as they are. Remains.
- a gold (Au) film is formed on the entire cross section of the device by a vacuum evaporation method (sputtering method) or an electroless plating method.
- the wiring electrode 45 connects a first thermoelectric body 15 and a second thermoelectric body 17 formed adjacent to each other in a cross section to form a thermocouple 50.
- thermoelectric elements in the composite thermoelectric structure 44 since the arrangement of the thermoelectric elements in the composite thermoelectric structure 44 is at a constant interval, the wiring of the thermoelectric elements is collectively performed by the wiring electrodes 45 without erroneous wiring. It is possible to do.
- thermoelectric body 15 of one of the synthetic thermoelectric structures and the second thermoelectric structure of the other are alternately laminated so as to face each other via a flat plate-shaped insulator 51 made of thermoelectric material 17 (see Fig. 41) and force acrylic resin, and bonded with an epoxy adhesive.
- the insulator 51 also provides mechanical strength to the entire thermoelectric generation unit so that the first thermoelectric body 15 and the second thermoelectric body 17 (see FIG. 41) do not make electrical contact. Play a role.
- the thickness of the insulator 51 is 50 ⁇ .
- an element end wiring 52 is formed at one end of each cross section of each composite thermoelectric structure 44 by using a conductive adhesive.
- the wire 2 may be a wire formed by a wire bonding method.
- the element end wiring 52 connects the ends of the thermoelectric elements 15 and 17 included in the composite thermoelectric structure 44. All the thermocouples 50 are connected in series. A thermoelectric generation unit is obtained. be able to.
- the wiring of the element end wiring 52 may be roughly compared with the precision required for forming the wiring electrode 45 formed on the wiring of the thermoelectric element in the above process. It can be done easily.
- thermoelectric power generation unit of the thirteenth embodiment the dry film of the photosensitive resin 12 formed by photolithography can be patterned with micron-order accuracy. is there,
- thermoelectric body 15 and the second thermoelectric body 17 which form the pattern along the patterned photosensitive resin 12a, 12b are formed with the accuracy of the order of micron. be able to.
- thermoelectric element formed by the plating method and the control of the composition are easy, and the pretreatment only for dissolving the raw materials is easier than before.
- the width of each thermoelectric element is 150 ⁇ and the space is 50 ⁇ as described above. At this time, the thickness including the insulator 51 is 150 ⁇ m.
- thermocouples 50 that can be formed on the substrate 10 is 2500 pairs.
- thermoelectric generator When a temperature difference of 2 ° C is given to this thermoelectric generator, an open-circuit voltage of about 2 V is obtained as an output, which is a sufficient output voltage for driving portable electronic devices such as watches.
- thermoelectric element Assuming that the length of this thermoelectric element is 2 mm, the internal impedance is about 13 k ⁇ , which is a sufficient order for electronic equipment.
- thermoelectric material or the dry film / polyimide
- the substrate 10 is made of a metal material, an iron plate, a nickel plate, a zinc plate, an aluminum plate, a titanium plate, a brass plate, or the like can be used. Further, a glass plate or a ceramic such as alumina can be used as the substrate 10.
- the electrode film 11 made of a titanium film formed on the ⁇ 0 substrate 10 can also be changed to a metal film other than the titanium film as long as the material is not dissolved in the plating solution.
- a gold (Au) film, a platinum (Pt) film, a palladium (Pd) film, a tantalum (Ta) film, or the like is an alternative to the titanium film. Effective.
- the wiring electrode 45 not only a gold (Au) film but also another metal film can be used.
- a printing method a method in which electrodes are patterned and attached to the surface of a separate plate-shaped material, and the like can be used.
- the element end wiring 52 can be formed by a method such as vacuum evaporation and sputtering of a metal film, a printing method, or a method in which an electrode having a patterned electrode on the surface of a plate-like material is attached. It can be used.
- a photosensitive material such as a photosensitive dry film can be used as a frame material when the thermoelectric material is to be used. Further, if the thickness of the plating film is about 10 ⁇ m, a rubber-based photoresist or a cinnamic acid-based photoresist can be used.
- the insulator 51 in addition to the above-described acrylic resin, any other material that is electrically insulated, has low thermal conductivity, and can easily maintain the temperature difference generated in the thermocouple can be used. It is possible to use. Epoxy resin can also be used as the insulator 51.
- the thickness of the thermoelectric body is set to half of the thickness of the photosensitive resin, but there is a deviation in fitting between the first matured electric structure 41 and the second thermoelectric structure 42. If it can be done without occurring,
- thermoelectric elements can be selected in a range that is smaller than the thickness of the photosensitive resin. INDUSTRIAL APPLICABILITY According to the method of manufacturing a thermoelectric power generation unit according to the present invention, a thermoelectric power generation unit that is ultra-small and has a sufficient output voltage can be easily and accurately manufactured.
- thermoelectric power generation unit can be widely used as a power source for extremely small portable electronic devices such as watches.
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Description
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Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
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US08/737,333 US5897330A (en) | 1994-05-16 | 1995-05-16 | Method of manufacturing thermoelectric power generation unit |
EP95918194A EP0760530B1 (en) | 1994-05-16 | 1995-05-16 | Manufacture of thermoelectric power generation unit |
DE69511263T DE69511263T2 (de) | 1994-05-16 | 1995-05-16 | Herstellung einer thermoelektrischen leistungserzeugungseinheit |
JP07529514A JP3115605B2 (ja) | 1994-05-16 | 1995-05-16 | 熱電発電ユニットの製造方法 |
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JP10139294 | 1994-05-16 | ||
JP6/101392 | 1994-05-16 |
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WO1995031832A1 true WO1995031832A1 (en) | 1995-11-23 |
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PCT/JP1995/000933 WO1995031832A1 (en) | 1994-05-16 | 1995-05-16 | Manufacture of thermoelectric power generation unit |
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US (1) | US5897330A (ja) |
EP (1) | EP0760530B1 (ja) |
JP (1) | JP3115605B2 (ja) |
CN (1) | CN1052345C (ja) |
DE (1) | DE69511263T2 (ja) |
WO (1) | WO1995031832A1 (ja) |
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KR20150021366A (ko) * | 2013-08-20 | 2015-03-02 | 엘지이노텍 주식회사 | 열전소자 및 이를 포함하는 열전모듈, 열전환장치 |
CN107623067B (zh) * | 2017-08-10 | 2019-11-12 | 南京航空航天大学 | 一种便携式高纵横比层间连接的微型垂直结构热电器件及其制备方法 |
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- 1995-05-16 JP JP07529514A patent/JP3115605B2/ja not_active Expired - Fee Related
- 1995-05-16 WO PCT/JP1995/000933 patent/WO1995031832A1/ja active IP Right Grant
- 1995-05-16 CN CN95193087A patent/CN1052345C/zh not_active Expired - Fee Related
- 1995-05-16 DE DE69511263T patent/DE69511263T2/de not_active Expired - Fee Related
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JP2007180455A (ja) * | 2005-12-28 | 2007-07-12 | Ritsumeikan | 熱電変換デバイス及び熱電変換デバイスの製造方法 |
JP2009528684A (ja) * | 2006-03-01 | 2009-08-06 | クラミック エレクトロニクス ゲーエムベーハー | ペルチェ素子精製プロセスとペルチェ素子 |
Also Published As
Publication number | Publication date |
---|---|
EP0760530A4 (en) | 1997-05-02 |
CN1148443A (zh) | 1997-04-23 |
EP0760530A1 (en) | 1997-03-05 |
EP0760530B1 (en) | 1999-08-04 |
DE69511263D1 (de) | 1999-09-09 |
JP3115605B2 (ja) | 2000-12-11 |
CN1052345C (zh) | 2000-05-10 |
DE69511263T2 (de) | 2000-01-13 |
US5897330A (en) | 1999-04-27 |
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