JPS63226980A - Manufacture of thermoelectric element for electronic wrist watch - Google Patents
Manufacture of thermoelectric element for electronic wrist watchInfo
- Publication number
- JPS63226980A JPS63226980A JP62060382A JP6038287A JPS63226980A JP S63226980 A JPS63226980 A JP S63226980A JP 62060382 A JP62060382 A JP 62060382A JP 6038287 A JP6038287 A JP 6038287A JP S63226980 A JPS63226980 A JP S63226980A
- Authority
- JP
- Japan
- Prior art keywords
- thermoelectric material
- thermoelectric
- substrate
- organic resin
- thermoelectric element
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 9
- 210000000707 wrist Anatomy 0.000 title 1
- 239000000463 material Substances 0.000 claims abstract description 44
- 239000000758 substrate Substances 0.000 claims abstract description 27
- 229920005989 resin Polymers 0.000 claims abstract description 16
- 239000011347 resin Substances 0.000 claims abstract description 16
- 238000005245 sintering Methods 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 9
- 238000005530 etching Methods 0.000 claims abstract description 8
- 239000002131 composite material Substances 0.000 claims abstract description 6
- 239000000843 powder Substances 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 239000011521 glass Substances 0.000 abstract description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052802 copper Inorganic materials 0.000 abstract description 3
- 239000010949 copper Substances 0.000 abstract description 3
- 238000004544 sputter deposition Methods 0.000 abstract description 3
- 239000011248 coating agent Substances 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 abstract description 2
- 238000000465 moulding Methods 0.000 abstract description 2
- 238000003825 pressing Methods 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 3
- 230000002265 prevention Effects 0.000 description 3
- 239000003990 capacitor Substances 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000036760 body temperature Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000012777 electrically insulating material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
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
- H10N10/80—Constructional details
- H10N10/85—Thermoelectric active materials
- H10N10/851—Thermoelectric active materials comprising inorganic compositions
- H10N10/853—Thermoelectric active materials comprising inorganic compositions comprising arsenic, antimony or bismuth
-
- 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
- H10N10/80—Constructional details
- H10N10/85—Thermoelectric active materials
- H10N10/851—Thermoelectric active materials comprising inorganic compositions
- H10N10/852—Thermoelectric active materials comprising inorganic compositions comprising tellurium, selenium or sulfur
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Electromechanical Clocks (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は電子腕時計において、熱を電力に変換し、２次
電池またはコンデンサの充電源として使用する熱電素子
の製造方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for manufacturing a thermoelectric element used in an electronic wristwatch to convert heat into electric power and to be used as a charging source for a secondary battery or a capacitor.
（発明の概要）
本発明は電子腕時計用熱電素子の製造方法において、表
面に熱電材料と反応しない物質を形成した基板に熱電材
料を加圧成形し、焼結した後、熱電材料を有機樹脂で被
覆補強し、次に基板をエツチングなどで除去して得た熱
電材料と有機樹脂の複合材料を用いることにより、利用
できる温度差が小さく微細な熱電材料片を数十個も直列
に結合する必要のある電子腕時計用熱電素子を高性能な
ものとしてしかも簡易に製造することを可能とするもの
である。(Summary of the Invention) The present invention provides a method for manufacturing a thermoelectric element for an electronic wristwatch, in which a thermoelectric material is pressure-molded onto a substrate on which a substance that does not react with the thermoelectric material is formed, and after sintering, the thermoelectric material is molded with an organic resin. By using a composite material of thermoelectric material and organic resin obtained by reinforcing the coating and then removing the substrate by etching, it is necessary to connect dozens of fine thermoelectric material pieces in series with small temperature difference. This makes it possible to easily manufacture a high-performance thermoelectric element for an electronic wristwatch.
電子腕時計において、体温と外気との温度差を利用して
熱電素子によりコンデンサや２次電池を充電して半永久
寿命電源が得られる。In an electronic wristwatch, a semi-permanent power source can be obtained by charging a capacitor or a secondary battery using a thermoelectric element using the temperature difference between body temperature and the outside air.
この場合、熱電材料としては（Ｂｉ、 ５ｂ）２（Ｓ１
３゜ＴＯ）ｓ系が最も優れているが、この材料でもＮ形
およびＰ形ともゼーベック係数は２００μＶ／に程度で
あり、腕時計のように生じる温度差は１〜２℃で、しか
も利用できる寸法も面積６−程度で、厚み１１程度の場
合、必要な電圧、約２Ｖ程度を得るためには、数十個の
熱電材料を直列に結合する必要があり、このような電子
腕時計用熱電素子を製造するには第４７回応用物理学会
学術講演予稿集（１９８６年）３８６頁２７Ｐ−ＺＨ−
４にみられるように厚膜的手法を利用することが考えら
れる。In this case, the thermoelectric material is (Bi, 5b)2(S1
The 3゜TO)s system is the best, but even with this material, the Seebeck coefficient for both N type and P type is about 200 μV/, and the temperature difference that occurs like a wristwatch is 1 to 2 degrees Celsius, and the size is available. If the area is about 6 mm and the thickness is about 11 mm, in order to obtain the necessary voltage of about 2 V, it is necessary to connect several dozen thermoelectric materials in series. How to manufacture 47th Japan Society of Applied Physics Academic Lecture Proceedings (1986) p. 386 27P-ZH-
It is conceivable to use a thick film method as shown in 4.
厚膜法で熱電材料を形成する場合、 （イ） 密度が小さく、導電率が小さい。 When forming thermoelectric materials using the thick film method, (a) Low density and low conductivity.
（ロ） ガラスなどの耐熱基板を使用する必要があり素
子にかかる温度差が小さくなる。(b) It is necessary to use a heat-resistant substrate such as glass, which reduces the temperature difference applied to the element.
というような欠点がある。There are drawbacks such as:
そこで本発明は上記のような欠点を解決し、電子腕時計
用熱電素子のように微細な熱電素子片を数千個も形成す
る必要のある熱電素子を簡易に、しかも高性能なものを
得ることを目的としている。Therefore, the present invention solves the above-mentioned drawbacks and provides a simple yet high-performance thermoelectric element that requires the formation of thousands of minute thermoelectric element pieces, such as thermoelectric elements for electronic wristwatches. It is an object.
（問題点を解決するための手段）
本発明では表面に焼結時に熱電材料と反応しない物質を
薄く形成した基板に熱電材料粉末を加圧成形し焼結後、
熱電材料を有機樹脂で被覆補強し基板をエツチングなど
により除去し、このようにして得た熱電材料と有機樹脂
の複合部材を用いて熱電素子を製造する。(Means for Solving the Problems) In the present invention, thermoelectric material powder is pressure-molded onto a substrate on which a thin substance that does not react with the thermoelectric material during sintering is formed on the surface, and after sintering,
The thermoelectric material is coated and reinforced with an organic resin, the substrate is removed by etching, etc., and a thermoelectric element is manufactured using the thus obtained composite member of the thermoelectric material and the organic resin.
上記のように加圧することで焼結後の熱電材料の密度が
向上し、導電率が向上する。By pressurizing as described above, the density of the thermoelectric material after sintering is improved, and the electrical conductivity is improved.
また基板に熱電材料と反応しない物質を形成することで
、金属板が基板として利用でき、ガラス基板やセラミッ
ク基板を使用するのとくらべて、加圧成形時の破壊が生
じない、薄板基板が容易に安価に入手できる、エツチン
グが容易などの利点を生じる。In addition, by forming a substance that does not react with thermoelectric materials on the substrate, a metal plate can be used as a substrate, and compared to using glass or ceramic substrates, it is easier to create thin substrates that do not break during pressure molding. It has advantages such as being inexpensively available and easily etched.
更に基板を除去し、有機樹脂で被覆することで素子の熱
伝導率を小さくでき、温度差が生じやすくなり、発生す
る電圧が大きくなる。Furthermore, by removing the substrate and covering it with an organic resin, the thermal conductivity of the element can be lowered, making it easier for temperature differences to occur and increasing the voltage generated.
以下図面により説明する。 This will be explained below with reference to the drawings.
第１図に示すように、熱電材料１を焼結時の反応を防止
するための反応防止層２を形成した基板３の上にプレス
４により加圧成形する。As shown in FIG. 1, a thermoelectric material 1 is pressure-molded by a press 4 onto a substrate 3 on which a reaction prevention layer 2 for preventing reactions during sintering is formed.
熱電材料は（Ｂｉ、 ５ｂ）ｚ （ｓｅ、 Ｔｅ）ｓ系
の粉末を用いる。反応防止層としてはスパッタなどによ
りガラス層などを形成する。As the thermoelectric material, (Bi, 5b)z (se, Te)s-based powder is used. As the reaction prevention layer, a glass layer or the like is formed by sputtering or the like.
基板としては銅板などが利用できる。銅板などを基板と
して使用することは、加圧時の破壊を防げ、また薄板を
簡単に得られるという利点があり、更にエツチングなど
も容易である。A copper plate or the like can be used as the substrate. The use of a copper plate or the like as a substrate has the advantage that it can be prevented from being destroyed when pressurized, and that a thin plate can be easily obtained, and furthermore, etching is easy.
このようにして基板上に形成された熱電材料は窒素雰囲
気中などで約４７０℃で焼結する。The thermoelectric material thus formed on the substrate is sintered at about 470° C. in a nitrogen atmosphere or the like.
焼結を行なった優、熱電材料の不必要な部分を除去する
などの操作を施し、たとえば第２図に示すように有機樹
脂５で熱電材料１を被覆補強する。After sintering, unnecessary portions of the thermoelectric material are removed, and the thermoelectric material 1 is covered and reinforced with an organic resin 5 as shown in FIG. 2, for example.
そのあとエツチングなどにより基板３を除去する。この
場合、反応防止層は熱電材料をエツチングの悪影響から
保護する８１能ももつ。Thereafter, the substrate 3 is removed by etching or the like. In this case, the anti-reaction layer also has the ability to protect the thermoelectric material from the adverse effects of etching.
このように有機樹脂と熱電材料が一体化された複合部材
は第３図に示すように積層され、熱電材料１が有機樹脂
５に周囲を埋められた形状で多数規則的に並べられ、Ｎ
形とＰ形が直列になるように電極を形成する。The composite member in which the organic resin and the thermoelectric material are integrated in this way is stacked as shown in FIG.
The electrodes are formed so that the shape and the P shape are in series.
電極はスパッタなどにより金属層を形成し、フォトリソ
グラフィにより所定のパターンとすることで形成できる
。The electrode can be formed by forming a metal layer by sputtering or the like and forming a predetermined pattern by photolithography.
このようにして最終的に完成した熱電素子は第４図に示
すように電極６に熱良導性物質で電気的に絶縁性をもつ
物質により絶縁層７を薄く形成し、熱の伝熱を良くする
ために伝熱板８を表面に設けた状態となる。As shown in Figure 4, the thermoelectric element finally completed in this way has a thin insulating layer 7 formed on the electrode 6 of a thermally conductive and electrically insulating material to reduce the heat transfer. In order to improve the quality, a heat exchanger plate 8 is provided on the surface.
上記のようにして断面積０．０１−で温度差方向の厚み
８厘の（Ｂｉ、 ５ｂ）２（Ｓｅ、 ＴＯ＞ｓ系熱電材
料をＮ形、Ｐ彫金わせて５０００個を０．２厘間隔で形
成しその問をエポキシ樹脂で埋めるような形で製造した
熱電素子を外気温２４℃で腕につけたところ、２．４１
Ｖの電圧が生じ、内部抵抗は５７．７にΩであった。As described above, (Bi, 5b)2(Se, TO>s thermoelectric material with a cross-sectional area of 0.01- and a thickness of 8 mm in the direction of temperature difference) was carved into N-shape and P-shape, and 5000 pieces were made into 0.2 mm. When a thermoelectric element manufactured by forming gaps and filling the gaps with epoxy resin was attached to the arm at an outside temperature of 24 degrees Celsius, the result was 2.41.
A voltage of V was developed and the internal resistance was 57.7Ω.
石英基板上に厚膜法により上記実施例と同様の材料と寸
法で、Ｎ形、Ｐ彫金わせて５０００個を形成し、石英基
板と熱電材料の間をエポキシ樹脂で埋めるような形で製
造した熱電素子を外気温２４℃で腕につけたところ、１
．０２Ｖの電圧が生じ、内部抵抗は２２５にΩであった
。A total of 5,000 N-shaped and P-shaped engravings were formed using the same materials and dimensions as in the above example on a quartz substrate using the thick film method, and the gap between the quartz substrate and the thermoelectric material was filled with epoxy resin. When I attached a thermoelectric element to my arm at an outside temperature of 24 degrees Celsius, 1
．． A voltage of 0.2 V was generated and the internal resistance was 225 Ω.
以上のように本発明の実施例による熱電素子は従来の厚
膜法によるものに比較して、発生する電圧が大きく内部
抵抗も小さく、これは熱電素子全体の熱伝導率の差によ
る生ずる温度差のちがい、および加圧による密度の向上
にともなう、導電率の向上に帰因する。As described above, the thermoelectric element according to the embodiment of the present invention generates a higher voltage and has a lower internal resistance than the thermoelectric element using the conventional thick film method, and this is due to the temperature difference caused by the difference in thermal conductivity of the entire thermoelectric element. This is due to the difference in electrical conductivity due to the difference in density and the increase in density due to pressurization.
上記のように本発明では、表面に熱電材料と反応しない
物質を形成した基板に熱電材料を加圧形成し、焼結し、
更にこれを有機樹脂で被覆補強してから基板を除去して
積層することにより高性能な電子腕時計用熱電素子を簡
易に製造することを可能とする。As described above, in the present invention, a thermoelectric material is formed under pressure on a substrate on which a substance that does not react with the thermoelectric material is formed, and then sintered.
Furthermore, by covering and reinforcing this with an organic resin, removing the substrate, and laminating it, it is possible to easily manufacture a high-performance thermoelectric element for an electronic wristwatch.
第１図から第３図までは熱電素子の製造工程を示す断面
図であり、第４図は熱電素子の部分断面図である。
１・・・熱電材料
２・・・反応防止層
３・・・基板
４・・・プレス
５・・・有機樹脂
６・・・電極
７・・・絶縁層
８・・・伝熱板1 to 3 are cross-sectional views showing the manufacturing process of the thermoelectric element, and FIG. 4 is a partial cross-sectional view of the thermoelectric element. 1... Thermoelectric material 2... Reaction prevention layer 3... Substrate 4... Press 5... Organic resin 6... Electrode 7... Insulating layer 8... Heat transfer plate
Claims (1)
た基板に熱電材料粉末を加圧形成し、焼結した後、熱電
材料を有機樹脂で被覆補強し、次に基板をエッチングな
どにより除去し、このようにして得た熱電材料と有機樹
脂の複合部材を用いて製造することを特徴とする電子腕
時計用熱電素子の製造方法。Thermoelectric material powder is formed under pressure on a substrate on which a thin substance that does not react with the thermoelectric material during sintering is formed, and after sintering, the thermoelectric material is coated and reinforced with an organic resin, and then the substrate is removed by etching. A method for manufacturing a thermoelectric element for an electronic wristwatch, characterized in that it is manufactured using a composite member of a thermoelectric material and an organic resin obtained in this way.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62060382A JPS63226980A (en) | 1987-03-16 | 1987-03-16 | Manufacture of thermoelectric element for electronic wrist watch |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62060382A JPS63226980A (en) | 1987-03-16 | 1987-03-16 | Manufacture of thermoelectric element for electronic wrist watch |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63226980A true JPS63226980A (en) | 1988-09-21 |
Family
ID=13140541
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62060382A Pending JPS63226980A (en) | 1987-03-16 | 1987-03-16 | Manufacture of thermoelectric element for electronic wrist watch |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63226980A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5246504A (en) * | 1988-11-15 | 1993-09-21 | Director-General, Agency Of Industrial Science And Technology | Thermoelectric material |
| EP0827215A2 (en) * | 1996-08-27 | 1998-03-04 | Kubota Corporation | Thermoelectric modules and thermoelectric elements |
| US8894792B2 (en) * | 2008-10-16 | 2014-11-25 | Korea Electrotechnology Research Institute | Manufacturing method of functional material using slice stack pressing process and functional material thereby |
| JP2019169702A (en) * | 2018-03-21 | 2019-10-03 | アールエムティー リミテッド | Method for manufacturing thermoelectric microcooler (variant) |
-
1987
- 1987-03-16 JP JP62060382A patent/JPS63226980A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5246504A (en) * | 1988-11-15 | 1993-09-21 | Director-General, Agency Of Industrial Science And Technology | Thermoelectric material |
| EP0827215A2 (en) * | 1996-08-27 | 1998-03-04 | Kubota Corporation | Thermoelectric modules and thermoelectric elements |
| EP0827215A3 (en) * | 1996-08-27 | 2000-09-20 | Kubota Corporation | Thermoelectric modules and thermoelectric elements |
| US8894792B2 (en) * | 2008-10-16 | 2014-11-25 | Korea Electrotechnology Research Institute | Manufacturing method of functional material using slice stack pressing process and functional material thereby |
| JP2019169702A (en) * | 2018-03-21 | 2019-10-03 | アールエムティー リミテッド | Method for manufacturing thermoelectric microcooler (variant) |
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