JPH1168177A - Manufacturing thermoelectric converter module - Google Patents

Manufacturing thermoelectric converter module

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Publication number
JPH1168177A
JPH1168177A JP9228693A JP22869397A JPH1168177A JP H1168177 A JPH1168177 A JP H1168177A JP 9228693 A JP9228693 A JP 9228693A JP 22869397 A JP22869397 A JP 22869397A JP H1168177 A JPH1168177 A JP H1168177A
Authority
JP
Japan
Prior art keywords
thermoelectric
thermoelectric semiconductor
conversion module
manufacturing
thermoelectric conversion
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.)
Granted
Application number
JP9228693A
Other languages
Japanese (ja)
Other versions
JP3724133B2 (en
Inventor
Takehiko Sato
岳彦 佐藤
Katsumoto Kamei
克基 亀井
Zenichi Shikada
善一 鹿田
Kentaro Kobayashi
健太郎 小林
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Panasonic Electric Works Co Ltd
Original Assignee
Matsushita Electric Works Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Matsushita Electric Works Ltd filed Critical Matsushita Electric Works Ltd
Priority to JP22869397A priority Critical patent/JP3724133B2/en
Publication of JPH1168177A publication Critical patent/JPH1168177A/en
Application granted granted Critical
Publication of JP3724133B2 publication Critical patent/JP3724133B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Abstract

PROBLEM TO BE SOLVED: To provide a method of manufacturing a thermoelectric converter module which has a low cost and high performance and reliability and allows the process to be simplified. SOLUTION: The manufacturing method comprises alternately disposing and bonding p- and n-type thermoelectric semiconductors 1, 2 through conductive bonding members 3 to form a block 4, cutting the block 4 approximately perpendicularly to the bond face of each thermoelectric semiconductor 1, 3 and bonding member 3 into small blocks 5 and mechanically removing a part of the bonding member 3 of the small block 5 to form electrodes 6 with the bonding member 3, using a dicing saw 7.

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【０００１】[0001]

【発明の属する技術分野】本発明は、ｐ形熱電半導体と
ｎ形熱電半導体とが電極により接合される熱電素子を複
数列設してユニット化した熱電変換モジュールの製造方
法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing a thermoelectric conversion module in which a plurality of thermoelectric elements in which a p-type thermoelectric semiconductor and an n-type thermoelectric semiconductor are joined by electrodes are arranged in a unit to form a unit.

【０００２】[0002]

【従来の技術】従来の積層型熱電変換モジュールは、ｐ
形熱電半導体とｎ形熱電半導体とを、導電性樹脂及び絶
縁層を介して交互に積層し一体化することにより製造さ
れている（特開平３−１１６７４号公報参照）。また、
その他の積層型熱電変換モジュールの製造方法として
は、ｐ形熱電半導体粉末とｎ形熱電半導体粉末とを、絶
縁性材料の粉末を介して積層し焼結することにより一体
化する方法が提案されている（特開平８−３２１２８号
公報参照）。2. Description of the Related Art A conventional laminated thermoelectric conversion module has a p-type.
It is manufactured by alternately stacking and integrating thermoelectric semiconductors and n-type thermoelectric semiconductors with a conductive resin and an insulating layer interposed therebetween (see Japanese Patent Application Laid-Open No. Hei 1111674). Also,
As another method for manufacturing a laminated thermoelectric conversion module, a method has been proposed in which a p-type thermoelectric semiconductor powder and an n-type thermoelectric semiconductor powder are laminated via an insulating material powder and sintered to be integrated. (See JP-A-8-32128).

【０００３】[0003]

【発明が解決しようとする課題】ところで、熱電変換モ
ジュールの製造にあたっては、モジュールの形状に応じ
て熱電半導体をチップ状もしくは板状などの形状に加工
する必要があるが、Ｂｉ−Ｔｅ−Ｓｂ−Ｓｅ系熱電半導
体は一般的に脆弱材料なので、熱電半導体インゴットを
切断する切断工程において材料の割れや欠けが発生した
り、寸法精度を整えるための工程が必要であり、材料歩
留りが低いという問題があった。また、これらの問題の
ため、素子形状（素子の幅や、素子の径など）の小型化
が難しく、高集積化やモジュールの小型化が難しいとい
う問題があり、高電圧低電流型の熱電変換モジュールの
製作が極めて難しいという問題があった。In manufacturing a thermoelectric conversion module, it is necessary to process a thermoelectric semiconductor into a chip shape or a plate shape according to the shape of the module. Since Se-based thermoelectric semiconductors are generally fragile materials, cracking or chipping of the material occurs in the cutting process of cutting the thermoelectric semiconductor ingot, and a process for adjusting dimensional accuracy is required, and the material yield is low. there were. In addition, due to these problems, it is difficult to miniaturize the element shape (element width, element diameter, and the like), and it is difficult to achieve high integration and module miniaturization. There was a problem that module fabrication was extremely difficult.

【０００４】また、熱電半導体は上述のように機械的強
度が弱いので、熱電半導体を小型化して配列する際に精
度の高い配列を行う場合、歩留りの低下やコストの増大
を招くという問題があった。また、上記従来の製造方法
では、各熱電半導体の両面にそれぞれ別々に電極を形成
するので電極形成の工程数が多く、しかも、電極と熱電
半導体との接合不良によって発生する導通不良や電極間
短絡が発生しやすく製品歩留りが低くなってしまうとい
う問題があった。さらに、従来の熱電変換モジュールで
は使用中に熱応力などのために電極と熱電半導体との間
にずれや剥離が生じたり、接合用の半田や熱電半導体の
劣化により性能が劣化してしまい、製品不良が生じやす
いという問題があった。また、従来の積層型熱電変換モ
ジュールの製造方法では、導電性樹脂と絶縁層とを分別
して塗布する必要があり工程が複雑になるとともに、導
電性樹脂の加熱硬化による応力が発生し熱電変換モジュ
ールの性能や信頼性が低下してしまう可能性があった。
また、焼結を行う場合に熱電半導体や導電性樹脂が高温
に耐えられないという不具合があった。Further, since the thermoelectric semiconductor has low mechanical strength as described above, there is a problem that when the thermoelectric semiconductor is miniaturized and arranged with high accuracy, the yield is reduced and the cost is increased. Was. In addition, in the above-described conventional manufacturing method, electrodes are separately formed on both surfaces of each thermoelectric semiconductor, so that the number of steps of electrode formation is large, and furthermore, conduction failure or short-circuit between electrodes caused by poor bonding between the electrodes and the thermoelectric semiconductor is caused. This is problematic in that the product yield tends to occur and the product yield decreases. Furthermore, in conventional thermoelectric conversion modules, the electrodes and the thermoelectric semiconductor are displaced or peeled off due to thermal stress during use, and the performance deteriorates due to the deterioration of the solder for bonding and the thermoelectric semiconductor. There is a problem that defects are likely to occur. In addition, in the conventional method for manufacturing a laminated thermoelectric conversion module, it is necessary to separately apply a conductive resin and an insulating layer, which complicates the process and generates stress due to heat curing of the conductive resin. There is a possibility that the performance and reliability of the device may be reduced.
Further, when sintering, there is a problem that the thermoelectric semiconductor or the conductive resin cannot withstand high temperatures.

【０００５】また、熱電変換モジュールに熱交換基板を
接合する場合、熱電変換モジュールの表面が平滑になっ
ている必要があるが、導電性樹脂や絶縁層の絶縁材が熱
電半導体の間からはみ出したり不足することにより、熱
電変換モジュールの表面が平滑にならないので、研削す
る必要があった。本発明は上記事由に鑑みて為されたも
のであり、その目的は、低コストで性能及び信頼性が高
く工程の簡略化が可能な熱電変換モジュールの製造方法
を提供することにある。When a heat exchange board is joined to a thermoelectric conversion module, the surface of the thermoelectric conversion module needs to be smooth. However, the conductive resin and the insulating material of the insulating layer may protrude from between thermoelectric semiconductors. Due to the shortage, the surface of the thermoelectric conversion module does not become smooth, so it was necessary to grind it. The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a method for manufacturing a thermoelectric conversion module that is low in cost, has high performance and reliability, and can simplify the process.

【０００６】[0006]

【課題を解決するための手段】請求項１の発明は、上記
目的を達成するために、ｐ形熱電半導体とｎ形熱電半導
体とが電極を介して同一方向に交互に配設されるととも
に接合され、かつ上記電極が該配設方向に直交する厚み
方向の両端側に交互に設けられる熱電変換モジュールの
製造方法であって、ｐ形熱電半導体とｎ形熱電半導体と
の間に導電性接合部材を設けて接合し一体化することに
よりブロック体を形成する第１の工程と、上記ブロック
体を各熱電半導体と導電性接合部材との接合面に対して
略直交するように切断することにより所望の厚さの小ブ
ロック体を形成する第２の工程と、小ブロック体の厚み
方向の一端側と他端側とから交互に導電性接合部材の一
部を除去することにより導電性接合部材よりなる上記電
極を形成する第３の工程とを有することを特徴とし、導
電性接合部材と各熱電半導体とを接合してブロック体を
形成した後にブロック体を所望の厚さに切断し、導電性
接合部材を部分的に除去することにより電極を形成する
ので、各熱電半導体を別々に所望の大きさに成形する必
要がなく、所望の大きさに成形された各熱電半導体を配
設する工程や各熱電半導体ごとに電極を接合するための
工程も不要となるから、製造工程の簡略化を図ることが
でき、歩留りを向上できるとともに、熱電変換モジュー
ルの低コスト化を図ることができる。また、導電性接合
部材のみを除去することにより電極を形成できるので、
比較的単価の高い熱電半導体を有効に利用することがで
きるとともに、熱電半導体の割れや破損が発生しにくく
材料歩留りや製品歩留りの向上を図ることができる。ま
た、第１の工程と第２の工程とにより熱電変換モジュー
ルのサイズが決まるので、熱電変換モジュールの形状の
制御が容易であり、熱電変換モジュールの小型化を図る
ことができるとともに、サイズの異なる熱電変換モジュ
ールを容易に作製することができる。さらに、熱電変換
モジュールの放熱面及び吸熱面となる小ブロック体の厚
み方向に直交する両面を略平滑に形成することができる
ので、放熱面及び吸熱面と熱交換基板もしくは熱交換器
との接合部の熱損失の減少を図ることができ、高性能で
信頼性の高い熱電変換モジュールを製造することができ
る。According to a first aspect of the present invention, in order to achieve the above object, a p-type thermoelectric semiconductor and an n-type thermoelectric semiconductor are alternately arranged in the same direction via an electrode and joined together. And a method of manufacturing a thermoelectric conversion module in which the electrodes are alternately provided on both ends in a thickness direction orthogonal to the disposing direction, wherein a conductive joining member is provided between the p-type thermoelectric semiconductor and the n-type thermoelectric semiconductor. A first step of forming a block body by providing, joining, and integrating, and cutting the block body so as to be substantially orthogonal to a bonding surface between each thermoelectric semiconductor and the conductive bonding member. A second step of forming a small block body having a thickness of 3 mm, and removing a portion of the conductive bonding member alternately from one end side and the other end side in the thickness direction of the small block body. Forming the above third electrode And bonding the conductive bonding member and each thermoelectric semiconductor to form a block body, cutting the block body to a desired thickness, and partially removing the conductive bonding member. Since the electrodes are formed, it is not necessary to separately mold each thermoelectric semiconductor into a desired size, and a process of arranging each thermoelectric semiconductor molded into a desired size and joining the electrodes for each thermoelectric semiconductor are performed. Therefore, the manufacturing process can be simplified, the yield can be improved, and the cost of the thermoelectric conversion module can be reduced. Also, since the electrode can be formed by removing only the conductive bonding member,
A thermoelectric semiconductor having a relatively high unit price can be effectively used, and the thermoelectric semiconductor is hardly cracked or damaged, and the material yield and the product yield can be improved. Further, since the size of the thermoelectric conversion module is determined by the first step and the second step, the shape of the thermoelectric conversion module can be easily controlled, and the size of the thermoelectric conversion module can be reduced, and the sizes of the thermoelectric conversion modules can be different. A thermoelectric conversion module can be easily manufactured. Furthermore, since both surfaces orthogonal to the thickness direction of the small block body serving as the heat-radiating surface and the heat-absorbing surface of the thermoelectric conversion module can be formed substantially smooth, the bonding between the heat-radiating surface and the heat-absorbing surface and the heat exchange substrate or the heat exchanger The heat loss of the part can be reduced, and a high-performance and highly reliable thermoelectric conversion module can be manufactured.

【０００７】請求項２の発明は、請求項１の発明におい
て、導電性接合部材として各熱電半導体と同程度の線膨
張率及び変形抵抗を有する金属を用い、導電性接合部材
と各熱電半導体とを押し出し加工により接合するので、
押し出し加工により導電性接合部材と各熱電半導体との
接合が行われるから、一括して導電性接合部材と各熱電
半導体とを接合することができる。また、各熱電半導体
と導電性接合部材との線膨張率が同程度であることか
ら、熱電変換モジュールへの通電時に電極の接合界面に
おける熱応力の発生を抑制することができ、信頼性が向
上する。また、各熱電半導体と導電性接合部材との変形
抵抗が同程度であるから、押し出し加工時の形状制御が
容易となる。また、導電性接合部材と各熱電半導体とを
押し出し加工により接合するので、押し出し材を切断す
ることで一度に大量のブロック体を形成することが可能
であり、生産性が向上する。According to a second aspect of the present invention, in the first aspect of the present invention, a metal having the same linear expansion coefficient and deformation resistance as each thermoelectric semiconductor is used as the conductive bonding member, and the conductive bonding member is connected to each thermoelectric semiconductor. Are joined by extrusion.
Since the conductive bonding member and each thermoelectric semiconductor are bonded by extrusion, the conductive bonding member and each thermoelectric semiconductor can be bonded together. In addition, since the coefficient of linear expansion between each thermoelectric semiconductor and the conductive bonding member is substantially the same, it is possible to suppress the occurrence of thermal stress at the bonding interface of the electrodes when power is supplied to the thermoelectric conversion module, thereby improving reliability. I do. Further, since the deformation resistance of each thermoelectric semiconductor and the conductive bonding member is substantially the same, the shape control at the time of extrusion is facilitated. Further, since the conductive joining member and each thermoelectric semiconductor are joined by extrusion, a large amount of blocks can be formed at once by cutting the extruded material, thereby improving productivity.

【０００８】請求項３の発明は、請求項２の発明におい
て、導電性接合部材を内部に複数の収納室が一方向に列
設されたカプセルとし、ｐ形熱電半導体粉末とｎ形熱電
半導体粉末とをカプセルの所定の収納室に充填した後
に、押し出し加工を行うことにより導電性接合部材と各
熱電半導体とを接合するので、押し出し形状の制御が容
易になるとともに、押し出し加工により押し出された熱
電半導体が多結晶になり、熱電半導体の機械的強度が向
上する。また、押し出し加工前の熱電半導体を粉末とし
たことにより押し出し加工時における熱電半導体の変形
抵抗が小さくなるので、押し出し速度が向上し生産性が
向上する。According to a third aspect of the present invention, in the second aspect of the present invention, the conductive bonding member is a capsule in which a plurality of storage chambers are arranged in one direction, and the p-type thermoelectric semiconductor powder and the n-type thermoelectric semiconductor powder are provided. After filling in the predetermined storage chamber of the capsule, the conductive joining member and each thermoelectric semiconductor are joined by performing the extrusion, so that the control of the extrusion shape is facilitated and the thermoelectric extruded by the extrusion is formed. The semiconductor becomes polycrystalline, and the mechanical strength of the thermoelectric semiconductor is improved. In addition, since the thermoelectric semiconductor before the extrusion is made into powder, the deformation resistance of the thermoelectric semiconductor during the extrusion is reduced, so that the extrusion speed is improved and the productivity is improved.

【０００９】請求項４の発明は、請求項２の発明におい
て、導電性接合部材を内部に複数の収納室が一方向に列
設されたカプセルとし、ｐ形熱電半導体圧粉体とｎ形熱
電半導体圧粉体とをカプセルの所定の収納室に充填した
後に、押し出し加工を行うことにより導電性接合部材と
各熱電半導体とを接合するので、押し出し加工前の熱電
半導体を圧粉体にしたことにより、粉末の場合に比べて
取扱いが容易になるとともに、熱電半導体の酸化を抑制
することができる。According to a fourth aspect of the present invention, in the second aspect of the present invention, the conductive bonding member is a capsule in which a plurality of storage chambers are arranged in one direction inside, and the p-type thermoelectric semiconductor compact and the n-type thermoelectric compact are formed. After the semiconductor green compact is filled in a predetermined storage chamber of the capsule, the conductive joining member and each thermoelectric semiconductor are joined by performing the extrusion, so that the thermoelectric semiconductor before the extrusion is formed into a green compact. Thereby, the handling is easier than in the case of powder, and the oxidation of the thermoelectric semiconductor can be suppressed.

【００１０】請求項５の発明は、請求項３又は請求項４
の発明において、押し出し加工後に、押し出された押し
出し部材を焼結するので、押し出し加工後に加熱処理が
行われるから、熱電半導体の強度の向上及び熱電半導体
と導電性接合部材との接合強度の向上が図られる。請求
項６の発明は、請求項１の発明において、導電性接合部
材として各熱電半導体と同程度の弾性率を有する金属を
用い、各熱電半導体として熱電半導体粉末を用い、ホッ
トプレスにより各熱電半導体と導電性接合部材とを接合
するので、加圧と焼結とが同時に行われるから、各熱電
半導体の機械的強度が向上し、結果として熱電変換モジ
ュールの機械的強度が向上する。また、ホットプレスを
行うことにより、各熱電半導体の結晶面が一軸に配向す
るので、各熱電半導体の熱電特性が向上する。[0010] The invention of claim 5 is the invention of claim 3 or claim 4.
In the invention of the above, since the extruded extruded member is sintered after the extruding process, the heat treatment is performed after the extruding process, so that the strength of the thermoelectric semiconductor and the bonding strength between the thermoelectric semiconductor and the conductive joining member are improved. It is planned. According to a sixth aspect of the present invention, in the first aspect, a metal having the same elastic modulus as each thermoelectric semiconductor is used as the conductive bonding member, a thermoelectric semiconductor powder is used as each thermoelectric semiconductor, and each thermoelectric semiconductor is hot-pressed. Since the pressure bonding and the sintering are performed at the same time, the mechanical strength of each thermoelectric semiconductor is improved, and as a result, the mechanical strength of the thermoelectric conversion module is improved. Further, by performing hot pressing, the crystal plane of each thermoelectric semiconductor is uniaxially oriented, so that the thermoelectric properties of each thermoelectric semiconductor are improved.

【００１１】請求項７の発明は、請求項１の発明におい
て、導電性接合部材として各熱電半導体と同程度の弾性
率を有する金属を用い、各熱電半導体として熱電半導体
粉末を用い、熱間静水圧プレスにより各熱電半導体と導
電性接合部材とを接合するので、加圧焼結によりネック
の再結合が促進され各熱電半導体の機械的強度が向上
し、結果として熱電変換モジュールの機械的強度が向上
する。According to a seventh aspect of the present invention, in the first aspect of the invention, a metal having substantially the same elastic modulus as each thermoelectric semiconductor is used as the conductive bonding member, and a thermoelectric semiconductor powder is used as each thermoelectric semiconductor. Since each thermoelectric semiconductor and the conductive joining member are joined by the hydraulic press, the recombination of the neck is promoted by the pressure sintering, and the mechanical strength of each thermoelectric semiconductor is improved. As a result, the mechanical strength of the thermoelectric conversion module is improved. improves.

【００１２】請求項８の発明は、請求項１の発明におい
て、各熱電半導体と導電性接合部材との間に、導電性を
有し且つ各熱電半導体へ拡散可能であって該拡散による
各熱電半導体の性能劣化の少ない導電性中間部材を介在
させてブロック体を形成するので、導電性中間部材の構
成元素が各熱電半導体に拡散することにより、各熱電半
導体の性能劣化なしに、各熱電半導体と導電性接合部材
との接合強度を高めることができる。According to an eighth aspect of the present invention, in the first aspect of the present invention, each thermoelectric semiconductor has a conductive property and can be diffused into each thermoelectric semiconductor between the thermoelectric semiconductor and the conductive joining member, and each thermoelectric semiconductor is formed by the diffusion. Since the block body is formed by interposing a conductive intermediate member with little deterioration in the performance of the semiconductor, the constituent elements of the conductive intermediate member diffuse into each thermoelectric semiconductor, so that each thermoelectric semiconductor does not deteriorate without the performance of each thermoelectric semiconductor. Bonding strength between the conductive member and the conductive bonding member can be increased.

【００１３】請求項９の発明は、請求項１又は請求項８
の発明において、各熱電半導体と導電性接合部材との間
に、導電性を有し且つ他の部材からの拡散を防止する拡
散防止部材を介在させてブロック体を形成するので、拡
散防止部材によって、この拡散防止部材を通る相互拡散
が抑制されるから、拡散による各熱電半導体と導電性接
合部材との接合強度の低下や熱電半導体の性能の経時劣
化を防止することができる。[0013] The invention of claim 9 is the invention of claim 1 or claim 8.
In the invention, since a block body is formed between each thermoelectric semiconductor and the conductive bonding member by interposing a diffusion preventing member having conductivity and preventing diffusion from other members, the diffusion preventing member Since the mutual diffusion through the diffusion preventing member is suppressed, it is possible to prevent a decrease in bonding strength between each thermoelectric semiconductor and the conductive bonding member due to the diffusion and a deterioration with time of the performance of the thermoelectric semiconductor.

【００１４】請求項１０の発明は、請求項２の発明にお
いて、各熱電半導体と導電性接合部材との間に、高い延
性を有する導電性中間部材を介在させて押し出し加工を
行うので、加圧接合時に接合界面に発生する応力を低減
できるから、押し出し形状の制御が容易になるととも
に、押し出し加工により形成されたブロック体を切断す
る工程における歩留りが向上する。According to a tenth aspect of the present invention, in the second aspect of the present invention, the extruding process is performed with a conductive intermediate member having high ductility interposed between each thermoelectric semiconductor and the conductive joining member. Since the stress generated at the joining interface during joining can be reduced, the extrusion shape can be easily controlled, and the yield in the step of cutting the block formed by the extrusion process can be improved.

【００１５】請求項１１の発明は、請求項１の発明にお
いて、導電性接合部材及び熱電半導体の少なくとも一方
の表面を、機械的切削、化学エッチング、サンドブラス
トなどにより粗面化した後に、各熱電半導体と導電性接
合部材とを接合するので、接合面の面積が増大し、接合
強度が向上する。請求項１２の発明は、請求項８又は請
求項１０の発明において、導電性中間部材を容器状に
し、該容器状に形成された導電性中間層材に熱電半導体
を充填した後にブロック体を形成するので、導電性中間
部材の厚さを均一にすることができるとともに、製造工
程の省力化を図ることができる。According to an eleventh aspect of the present invention, in the first aspect of the invention, at least one of the surfaces of the conductive bonding member and the thermoelectric semiconductor is roughened by mechanical cutting, chemical etching, sand blasting, or the like, and then each thermoelectric semiconductor is formed. And the conductive joining member, the area of the joining surface increases, and the joining strength improves. According to a twelfth aspect of the present invention, in the invention of the eighth or tenth aspect, the conductive intermediate member is formed into a container, and the conductive intermediate material formed in the container is filled with a thermoelectric semiconductor to form a block body. Therefore, the thickness of the conductive intermediate member can be made uniform, and the manufacturing process can be labor-saving.

【００１６】請求項１３の発明は、請求項８又は請求項
１０又は請求項１１の発明において、ブロック体を形成
する前に、導電性接合部材の表面に、メッキ、スパッタ
リング、ペースト塗布等のいずれかの方法により導電性
中間部材を形成する工程を有するので、導電性接合部材
と導電性中間層部材との接合強度が向上する。請求項１
４の発明は、請求項８又は請求項１０又は請求項１１の
発明において、ブロック体を形成する前に、各熱電半導
体の表面に、メッキ、スパッタリング、ペースト塗布等
のいずれかの方法により導電性中間部材を形成する工程
を有するので、導電性接合部材と導電性中間層部材との
接合強度が向上する。According to a thirteenth aspect of the present invention, in any one of the eighth, tenth, and eleventh aspects of the present invention, any one of plating, sputtering, paste application, and the like is applied to the surface of the conductive bonding member before the block body is formed. Since the method includes the step of forming the conductive intermediate member by the above method, the bonding strength between the conductive bonding member and the conductive intermediate layer member is improved. Claim 1
According to a fourth aspect of the present invention, in the invention of the eighth aspect, the tenth aspect or the eleventh aspect, the conductive material is formed on the surface of each thermoelectric semiconductor by any method such as plating, sputtering, or paste application before forming the block body. Since the step of forming the intermediate member is included, the bonding strength between the conductive bonding member and the conductive intermediate layer member is improved.

【００１７】請求項１５の発明は、請求項１の発明にお
いて、上記第３の工程は、導電性接合部材の一部をダイ
シングソーなどを用いた機械加工により除去するので、
加工時間を短くできるとともに熱負荷が小さく、生産性
が向上する。請求項１６の発明は、請求項１の発明にお
いて、上記第３の工程は、導電性接合部材の一部をレー
ザにより除去するので、請求項１５の発明に比べて微細
加工が可能となり、熱電変換モジュールの小型化が可能
となる。According to a fifteenth aspect of the present invention, in the first aspect, the third step removes a part of the conductive bonding member by machining using a dicing saw or the like.
The processing time can be shortened, the heat load is small, and the productivity is improved. According to a sixteenth aspect of the present invention, in the first aspect of the present invention, in the third step, a part of the conductive bonding member is removed by a laser. The conversion module can be reduced in size.

【００１８】請求項１７の発明は、請求項１の発明にお
いて、上記第３の工程は、小ブロック体を導電性接合部
材の除去部が開孔されたマスクを設けた後に、サンドブ
ラストにより導電性接合部材の一部を除去するので、マ
スクを併用することにより広範囲での加工が可能とな
り、生産性が向上する。請求項１８の発明は、請求項１
の発明において、熱電変換モジュールへの通電時に各熱
電半導体の結晶面が通電方向に対して平行に配向するよ
うに各熱電半導体を形成するので、熱電半導体の性能が
高くなる方向と熱電半導体への通電方向とが一致するか
ら、熱電変換モジュールの性能が向上する。According to a seventeenth aspect of the present invention, in the first aspect of the present invention, in the third step, after the small block body is provided with a mask in which the removed portion of the conductive bonding member is opened, the small block body is subjected to conductive blasting by sandblasting. Since a part of the joining member is removed, processing can be performed in a wide range by using a mask in combination, thereby improving productivity. The invention of claim 18 is based on claim 1
In the invention of (1), when the thermoelectric conversion module is energized, each thermoelectric semiconductor is formed such that the crystal plane of each thermoelectric semiconductor is oriented in parallel to the energization direction. Since the energization direction matches, the performance of the thermoelectric conversion module is improved.

【００１９】請求項１９の発明は、請求項１の発明にお
いて、導電性接合部材が除去された除去部を樹脂などの
絶縁性材料で充填するので、熱電半導体の強度及び電極
の接合強度が向上し、耐衝撃性、耐振動性が向上し、防
湿、酸化防止、電気絶縁、ホイスカー発生抑制などを図
ることができる。請求項２０の発明は、請求項１９の発
明において、絶縁性材料として熱伝導率が略０．０１Ｗ
／ｍＫ乃至略０．５Ｗ／ｍＫの低熱伝導率材料を使用す
るので、熱電変換モジュールの吸熱面と放熱面との間の
熱短絡が抑制され、熱電変換モジュールの性能が向上す
る。According to a nineteenth aspect, in the first aspect, the removed portion from which the conductive bonding member is removed is filled with an insulating material such as a resin, so that the strength of the thermoelectric semiconductor and the bonding strength of the electrode are improved. In addition, shock resistance and vibration resistance are improved, and moisture proof, oxidation prevention, electric insulation, whisker generation suppression, and the like can be achieved. According to a twentieth aspect, in the nineteenth aspect, the thermal conductivity of the insulating material is approximately 0.01 W.
Since a low thermal conductivity material of about / mK to about 0.5 W / mK is used, a thermal short circuit between the heat absorbing surface and the heat radiating surface of the thermoelectric conversion module is suppressed, and the performance of the thermoelectric conversion module is improved.

【００２０】請求項２１の発明は、請求項１９の発明に
おいて、絶縁性材料としてシリコーン樹脂のような柔軟
性のある材料を使用するので、熱電変換モジュールへの
通電時に発生する熱応力が緩和されるとともに、耐衝撃
性が向上するから、熱電変換モジュールの信頼性が向上
する。請求項２２の発明は、請求項１９の発明におい
て、絶縁性材料としてエポキシ樹脂のような熱電半導体
との接合強度が熱電半導体の引っ張り強度以上の高接着
性樹脂を使用するので、絶縁性材料と熱電半導体との接
合強度が向上し、絶縁性材料の剥離や脱落を防止するこ
とができる。According to a twenty-first aspect of the present invention, since a flexible material such as a silicone resin is used as the insulating material in the nineteenth aspect of the invention, thermal stress generated when power is supplied to the thermoelectric conversion module is reduced. In addition, since the shock resistance is improved, the reliability of the thermoelectric conversion module is improved. According to a twenty-second aspect of the present invention, in the nineteenth aspect of the present invention, a high adhesive resin having a bonding strength to a thermoelectric semiconductor such as an epoxy resin that is equal to or greater than the tensile strength of the thermoelectric semiconductor is used as the insulating material. The bonding strength with the thermoelectric semiconductor is improved, and peeling or falling off of the insulating material can be prevented.

【００２１】請求項２３の発明は、請求項１９の発明に
おいて、絶縁性材料として３００℃以上の耐熱性を有す
るエポキシ樹脂やポリイミド樹脂のような高耐熱性材料
を使用するので、絶縁性材料の耐熱性が向上して信頼性
が向上する。また、熱電変換モジュールが焼損する場合
も容易に発火しないので、安全性が向上する。請求項２
４の発明は、請求項１９乃至請求項２３の発明におい
て、上記除去部を絶縁性材料で充填する前に、化学的エ
ッチング、サンドブラスト等により各熱電半導体の表面
を粗面化するので、接合部でのアンカー効果が大きくな
り、絶縁性材料の接合強度が向上する。According to a twenty-third aspect of the present invention, in the nineteenth aspect, a high heat-resistant material such as an epoxy resin or a polyimide resin having a heat resistance of 300 ° C. or more is used as the insulating material. Heat resistance is improved and reliability is improved. In addition, even if the thermoelectric conversion module is burned, it is not easily ignited, so that safety is improved. Claim 2
According to a fourth aspect of the present invention, the surface of each thermoelectric semiconductor is roughened by chemical etching, sand blasting or the like before filling the removed portion with an insulating material. In this case, the anchor effect is increased, and the bonding strength of the insulating material is improved.

【００２２】請求項２５の発明は、請求項１又は請求項
１９の発明において、上記第１、第２、第３の工程によ
り形成された熱電変換モジュールの厚み方向の両面にお
ける電極及び各熱電半導体の表面に熱伝導率の高い金属
薄膜を形成する工程を有するので、熱電変換モジュール
の厚み方向の両面における電極及び各熱電半導体の表面
に熱伝導率の高い金属薄膜を形成することにより、放熱
板もしくは絶縁板との良好な熱伝導性を得ることができ
るとともに、電極の接合部の熱応力を緩和することがで
きる。また、熱電半導体や電極の表面の酸化を抑制する
とともに防湿性を高めることができる。According to a twenty-fifth aspect of the present invention, in the first or the nineteenth aspect, electrodes and thermoelectric semiconductors on both surfaces in the thickness direction of the thermoelectric conversion module formed by the first, second, and third steps are provided. Forming a metal thin film with high thermal conductivity on the surface of the thermoelectric conversion module by forming a metal thin film with high thermal conductivity on the surface of the electrodes and each thermoelectric semiconductor on both sides in the thickness direction of the thermoelectric conversion module. Alternatively, good thermal conductivity with the insulating plate can be obtained, and the thermal stress at the joint of the electrodes can be reduced. In addition, it is possible to suppress oxidation of the surface of the thermoelectric semiconductor or the electrode and to improve moisture proofness.

【００２３】請求項２６の発明は、請求項１又は請求項
１９の発明において、上記第１、第２、第３の工程によ
り形成された熱電変換モジュールの厚み方向の両面にお
ける電極及び各熱電半導体の表面に導電性薄膜を形成も
しくは導電性薄板を接合する工程を有するので、熱電変
換モジュールの厚み方向の両面における電極及び各熱電
半導体の表面に導電性薄膜又は導電性薄板を設けること
により、電極の接合強度を高めることができ、さらに、
電極への電流の集中を抑制することができる。また、熱
電半導体や電極の表面の酸化を抑制するとともに防湿性
を高めることができる。According to a twenty-sixth aspect of the present invention, in the first or the nineteenth aspect, the electrodes and the thermoelectric semiconductors on both surfaces in the thickness direction of the thermoelectric conversion module formed by the first, second, and third steps are provided. Since a step of forming a conductive thin film on the surface of the thermoelectric conversion module or bonding the conductive thin plate is provided, by providing the conductive thin film or the conductive thin plate on the surface of each of the electrodes and each thermoelectric semiconductor on both surfaces in the thickness direction of the thermoelectric conversion module, Can increase the bonding strength of
Concentration of current on the electrodes can be suppressed. In addition, it is possible to suppress oxidation of the surface of the thermoelectric semiconductor or the electrode and to improve moisture proofness.

【００２４】請求項２７の発明は、請求項１又は請求項
１９又は請求項２５又は請求項２６の発明において、上
記第１、第２、第３の工程により形成された熱電変換モ
ジュールの全面に樹脂等の絶縁性材料をコーティングす
る工程を有するので、熱電変換モジュールの全面に絶縁
性材料をコーティングすることにより、放熱板や吸熱板
など熱交換器との電気絶縁性を高めることができるとと
もに、熱電半導体や電極の表面の酸化を抑制でき、さら
に、防湿性を高めることができる。According to a twenty-seventh aspect of the present invention, in the first or the nineteenth aspect, the twenty-fifth or the twenty-sixth aspect of the present invention, the entire surface of the thermoelectric conversion module formed by the first, second, and third steps is provided. Since it has a process of coating an insulating material such as a resin, by coating the entire surface of the thermoelectric conversion module with an insulating material, it is possible to enhance electrical insulation with a heat exchanger such as a heat sink or a heat absorbing plate. Oxidation of the surface of the thermoelectric semiconductor or the electrode can be suppressed, and the moisture resistance can be further improved.

【００２５】[0025]

【発明の実施の形態】BEST MODE FOR CARRYING OUT THE INVENTION

（実施形態１）本実施形態の熱電変換モジュールの製造
方法を図１に基づいて説明する。なお、熱電半導体の材
料としては、ｐ形熱電半導体１は（Ｓｂ，Ｂｉ）2 （Ｔ
ｅ，Ｓｅ）3 を主成分とし、ｎ形熱電半導体２はＢｉ2
（Ｔｅ，Ｓｅ）3 を主成分としている。(Embodiment 1) A method for manufacturing a thermoelectric conversion module of this embodiment will be described with reference to FIG. As a material of the thermoelectric semiconductor, the p-type thermoelectric semiconductor 1 is (Sb, Bi) 2 (T
e, Se) 3 as the main component, and the n-type thermoelectric semiconductor 2 is made of Bi 2
(Te, Se) 3 is a main component.

【００２６】本実施形態では、まず、図１（ａ）に示す
ように、矩形板状のｐ形熱電半導体１と、矩形板状のｎ
形熱電半導体２とを、矩形板状であって熱伝導率の高い
（例えば、Ａｌ製やＡｌ合金製の）導電性接合部材３を
介して接合する（例えば、押し出し、ホットプレス、熱
間静水圧プレスなどにより接合する）ことによって、ｐ
形熱電半導体１とｎ形熱電半導体２とが導電性接合部材
３を介して交互に配設されたブロック体４を形成する。
すなわち、ブロック体４は、各部材が、導電性接合部材
３、ｐ形熱電半導体１、導電性接合部材３、ｎ形熱電半
導体２、導電性接合部材３、ｐ形熱電半導体１、・・
・、導電性接合部材３の順に図１（ａ）の左右方向に積
層されている。なお、本実施形態では、各熱電半導体
１，２の厚さを略０．５ｍｍ、導電性接合部材３の厚さ
を略０．２ｍｍとし、各部材１，２，３の縦寸法（図１
（ａ）のブロック体４の上下方向の寸法）及び幅寸法
（図１（ａ）のブロック体４の奥行きの寸法）は同一に
してあり、上記縦寸法は１０〜５００ｍｍ程度、上記幅
寸法は５ｍｍ程度にしてある。In this embodiment, first, as shown in FIG. 1A, a rectangular plate-shaped p-type thermoelectric semiconductor 1 and a rectangular plate-shaped n-type thermoelectric semiconductor 1 are formed.
The thermoelectric semiconductor 2 is joined (for example, extruded, hot pressed, hot static) to a rectangular plate-shaped conductive joining member 3 having a high thermal conductivity (for example, made of Al or Al alloy). Bonding by a hydraulic press, etc.)
The block body 4 in which the thermoelectric semiconductors 1 and the n-type thermoelectric semiconductors 2 are alternately arranged via the conductive bonding members 3 is formed.
That is, in the block body 4, each member is composed of the conductive bonding member 3, the p-type thermoelectric semiconductor 1, the conductive bonding member 3, the n-type thermoelectric semiconductor 2, the conductive bonding member 3, the p-type thermoelectric semiconductor 1,.
1, the conductive bonding members 3 are stacked in the left-right direction in FIG. In this embodiment, the thickness of each thermoelectric semiconductor 1, 2 is approximately 0.5 mm, the thickness of the conductive bonding member 3 is approximately 0.2 mm, and the vertical dimension of each member 1, 2, 3 (FIG.
The vertical dimension of the block body 4 in (a) and the width dimension (the depth dimension of the block body 4 in FIG. 1A) are the same, the vertical dimension is about 10 to 500 mm, and the width dimension is It is about 5 mm.

【００２７】図１（ａ）のブロック体４を形成した後
は、ダイシングソーなどによってブロック体４を図１
（ｂ）に示すように各熱電半導体１，２それぞれと導電
性接合部材３との接合面に対して横断するように切断す
る（スライスする）ことにより、複数の矩形板状の小ブ
ロック体５を形成する。なお、本実施形態では、各小ブ
ロック体５は、厚さが２．０ｍｍ程度のなるように切断
する。また、本実施形態では、ｐ形熱電半導体１、ｎ形
熱電半導体２、導電性接合部材３及びブロック体４の幅
寸法を５．０ｍｍにしてあるが、例えば幅寸法が１５ｍ
ｍ程度のブロック体４’を形成した後に、幅寸法が５．
０ｍｍになるようにブロック体４’を切断してブロック
体４を形成してもよい。After the block 4 shown in FIG. 1A is formed, the block 4 is removed by a dicing saw or the like.
As shown in (b), a plurality of rectangular plate-shaped small block bodies 5 are cut by cutting (slicing) the thermoelectric semiconductors 1 and 2 so as to cross the bonding surface between the conductive bonding member 3 and each of them. To form In this embodiment, each small block body 5 is cut so as to have a thickness of about 2.0 mm. In the present embodiment, the width of the p-type thermoelectric semiconductor 1, the n-type thermoelectric semiconductor 2, the conductive bonding member 3, and the block 4 is set to 5.0 mm.
After forming about 4 m block body 4 ′, the width dimension is 5.
The block 4 ′ may be formed by cutting the block 4 ′ so as to be 0 mm.

【００２８】図１（ｂ）の小ブロック体５を形成した後
は、図１（ｃ）に示すように、小ブロック体５の導電性
接合部材３の一部を、小ブロック体５の厚み方向に対し
て、例えば刃部の材料にダイヤモンドを用いたダイシン
グソー７によって機械的に除去する。以後、この除去工
程により残った部分の導電性接合部材３を電極６と称
す。ところで、各導電性接合部材３は、交互に、小ブロ
ック体５の厚み方向の反対側が一部除去される。すなわ
ち、図１（ｃ）に示すように導電性接合部材３を１枚お
きに小ブロック体５の下部において導電性接合部材３よ
りなる電極６が残るように除去し、さらに、電極６間に
存在する導電性接合部材３を小ブロック体５の上部にお
いて導電性接合部材３よりなる電極６が残るように除去
することによって、図１（ｄ）に示すような熱電変換モ
ジュール１００が形成される。After forming the small block body 5 in FIG. 1B, as shown in FIG. 1C, a part of the conductive joining member 3 of the small block body 5 is In the direction, for example, it is mechanically removed by a dicing saw 7 using diamond as a material of the blade portion. Hereinafter, the portion of the conductive bonding member 3 remaining after this removing step is referred to as an electrode 6. By the way, in each of the conductive bonding members 3, the opposite side in the thickness direction of the small block body 5 is partially removed alternately. That is, as shown in FIG. 1C, every other conductive bonding member 3 is removed so that the electrode 6 made of the conductive bonding member 3 remains under the small block body 5, and furthermore, between the electrodes 6. The thermoelectric conversion module 100 as shown in FIG. 1D is formed by removing the existing conductive bonding member 3 so that the electrode 6 made of the conductive bonding member 3 remains above the small block body 5. .

【００２９】ここに、熱電変換モジュール１００は、図
１（ｄ）に示すように、複数のｐ形熱電半導体１と複数
のｎ形熱電半導体２とが、電極６、ｐ形熱電半導体１、
電極６、ｎ形熱電半導体２、電極６、ｐ形熱電半導体
１、電極６、ｎ形熱電半導体２、・・・、電極６の順で
配設されており、ｐ形熱電半導体１とｎ形熱電半導体２
とが交互に直列接続される。Here, in the thermoelectric conversion module 100, as shown in FIG. 1 (d), a plurality of p-type thermoelectric semiconductors 1 and a plurality of n-type thermoelectric semiconductors 2 are composed of an electrode 6, a p-type thermoelectric semiconductor 1,
The electrode 6, the n-type thermoelectric semiconductor 2, the electrode 6, the p-type thermoelectric semiconductor 1, the electrode 6, the n-type thermoelectric semiconductor 2,..., The electrode 6 are arranged in this order, and the p-type thermoelectric semiconductor 1 and the n-type Thermoelectric semiconductor 2
Are alternately connected in series.

【００３０】ところで、ダイシングソー７の刃部の厚さ
を導電性接合部材３の厚さと同程度にしておけば、両熱
電半導体１，２を過剰に削除することなく、１度の位置
決めで導電性接合部材３の上記一部の除去を行うことが
できる。また、複数のダイシングソー７を両熱電半導体
１，２の厚さで決まる所定間隔で配置し、一度に複数の
導電性接合部材３の上記一部の除去を行えば、除去工程
に要する時間を短縮することができる。By the way, if the thickness of the blade portion of the dicing saw 7 is set to be substantially the same as the thickness of the conductive joining member 3, the conductive positioning can be performed by one-time positioning without excessively removing the thermoelectric semiconductors 1 and 2. The above-mentioned part of the sex bonding member 3 can be removed. In addition, if a plurality of dicing saws 7 are arranged at predetermined intervals determined by the thicknesses of the thermoelectric semiconductors 1 and 2 and the above-mentioned portions of the plurality of conductive bonding members 3 are removed at a time, the time required for the removal step is reduced. Can be shortened.

【００３１】しかして、本実施形態では、導電性接合部
材３と各熱電半導体１，２とを接合してブロック体４を
形成した後にブロック体４を所望の厚さに切断して小ブ
ロッ体５を形成し、小ブロック体５の導電性接合部材３
を部分的に除去することにより電極６を形成するので、
従来のように各熱電半導体１，２を別々に所望の大きさ
に成形する必要がなく、所望の大きさに成形された各熱
電半導体１，２を配設する工程や各熱電半導体１，２ご
とに電極６を接合するための工程も不要となるから、製
造工程の簡略化を図ることができ、歩留りを向上できる
とともに、熱電変換モジュール１００の低コスト化を図
ることができる。また、導電性接合部材３のみを除去す
ることにより電極６を形成できるので、比較的単価の高
い熱電半導体１，２を有効に利用することができるとと
もに、熱電半導体１，２の割れや破損が発生しにくく材
料歩留りや製品歩留りの向上を図ることができる。ま
た、ブロック体４を形成する工程と、小ブロック体５を
形成する工程とにより熱電変換モジュール１００のサイ
ズが決まるので、熱電変換モジュール１００の形状の制
御が容易であり、熱電変換モジュール１００の小型化を
図ることができるとともに、サイズの異なる熱電変換モ
ジュール１００を容易に作製することができる。さら
に、熱電変換モジュール１００の放熱面及び吸熱面とな
る厚み方向に直交する両面を略平滑に形成することがで
きるので、放熱面及び吸熱面と熱交換基板もしくは熱交
換器との接合部の熱損失の減少を図ることができ、高性
能で信頼性の高い熱電変換モジュール１００を製造する
ことができる。In the present embodiment, the conductive bonding member 3 and the thermoelectric semiconductors 1 and 2 are bonded together to form the block 4 and then the block 4 is cut into a desired thickness to form a small block. 5 and the conductive joining member 3 of the small block body 5
To form the electrode 6 by partially removing
There is no need to separately mold the thermoelectric semiconductors 1 and 2 to a desired size as in the related art. Since a process for bonding the electrodes 6 is not required for each process, the manufacturing process can be simplified, the yield can be improved, and the cost of the thermoelectric conversion module 100 can be reduced. Further, since the electrode 6 can be formed by removing only the conductive bonding member 3, the thermoelectric semiconductors 1, 2 having a relatively high unit price can be effectively used, and the thermoelectric semiconductors 1, 2 can be cracked or damaged. It is hard to occur, and the material yield and the product yield can be improved. In addition, since the size of the thermoelectric conversion module 100 is determined by the step of forming the block body 4 and the step of forming the small block body 5, the shape of the thermoelectric conversion module 100 can be easily controlled, and the size of the thermoelectric conversion module 100 can be reduced. The thermoelectric conversion modules 100 having different sizes can be easily manufactured. Further, since both surfaces perpendicular to the thickness direction of the heat dissipation surface and the heat absorption surface of the thermoelectric conversion module 100 can be formed substantially smooth, the heat of the junction between the heat dissipation surface and the heat absorption surface and the heat exchange substrate or the heat exchanger can be obtained. The loss can be reduced, and the thermoelectric conversion module 100 with high performance and high reliability can be manufactured.

【００３２】また、本実施形態では、導電性接合部材３
をダイシングソー７などによって除去するので、加工時
間を短くできるとともに熱負荷が小さく、生産性が向上
する。なお、本実施形態では、各熱電半導体１，２及び
導電性接合部材３の形状が矩形板状である場合について
説明したが、こらら各部材１，２，３は、棒状（角柱
状）であってもよい。In the present embodiment, the conductive bonding member 3
Is removed by the dicing saw 7 or the like, so that the processing time can be shortened, the heat load is reduced, and the productivity is improved. In the present embodiment, the case where the thermoelectric semiconductors 1 and 2 and the conductive bonding member 3 have a rectangular plate shape has been described. There may be.

【００３３】（実施形態２）本実施形態の熱電変換モジ
ュールの製造方法を図２に基づいて説明する。本実施形
態は、ｐ形熱電半導体１、ｎ形熱電半導体２、導電性接
合部材３を押し出し加工により接合する点に特徴があ
り、それ以外の製造方法については実施形態１と同様で
あるから説明は省略する。(Embodiment 2) A method of manufacturing a thermoelectric conversion module according to this embodiment will be described with reference to FIG. The present embodiment is characterized in that the p-type thermoelectric semiconductor 1, the n-type thermoelectric semiconductor 2, and the conductive bonding member 3 are bonded by extrusion, and the other manufacturing method is the same as that of the first embodiment, and will be described. Is omitted.

【００３４】本実施形態では、まず、図２（ａ）に示す
ように有底筒状のＡｌ製のカプセル８に熱電半導体粉末
を充填する。ここに、カプセル８は、カプセル８に一体
形成されカプセル８の軸方向に平行な複数の仕切壁８ｂ
によって内部空間が複数の短冊状の充填孔８ａ（収納
室）に分割されており、粒径が１０〜５００μｍ程度の
ｐ形熱電半導体粉末１’及びｎ形熱電半導体粉末２’
を、充填孔８ａに交互に充填する。つまり、ある充填孔
８ａにｐ形熱電半導体粉末１’を充填した場合には、そ
の隣接する充填孔８ａにはｎ形熱電半導体粉末２’を充
填する。なお、本実施形態におけるカプセル８の形状
は、外径を６８．０ｍｍ、軸方向の長さ（高さ）を３０
０ｍｍとし、充填孔８ａは短辺の長さを２．２４ｍｍ、
長辺の長さを２２．４ｍｍ、深さを２００ｍｍとし、充
填孔８ａ間の距離（つまり、仕切壁８ｂの厚さ）を０．
８９ｍｍとしてあるが、カプセル８の形状や寸法は特に
限定するものではなく、押し出し加工機のコンテナの形
状や押し出し比に依存し、充填孔８ａの形状や寸法はカ
プセル８の形状に応じて適宜設定することができる。In this embodiment, first, as shown in FIG. 2A, a thermoelectric semiconductor powder is filled in a bottomed cylindrical capsule 8 made of Al. Here, the capsule 8 includes a plurality of partition walls 8 b formed integrally with the capsule 8 and parallel to the axial direction of the capsule 8.
The internal space is divided into a plurality of strip-shaped filling holes 8a (storage chambers), and the p-type thermoelectric semiconductor powder 1 ′ and the n-type thermoelectric semiconductor powder 2 ′ having a particle size of about 10 to 500 μm.
Are alternately filled in the filling holes 8a. That is, when a certain filling hole 8a is filled with the p-type thermoelectric semiconductor powder 1 ', the adjacent filling hole 8a is filled with the n-type thermoelectric semiconductor powder 2'. In addition, the shape of the capsule 8 in the present embodiment has an outer diameter of 68.0 mm and an axial length (height) of 30.
0 mm, the filling hole 8a has a short side length of 2.24 mm,
The length of the long side is 22.4 mm, the depth is 200 mm, and the distance between the filling holes 8a (that is, the thickness of the partition wall 8b) is 0.
Although it is set to 89 mm, the shape and size of the capsule 8 are not particularly limited, and depend on the shape and extrusion ratio of the container of the extruder, and the shape and size of the filling hole 8 a are appropriately set according to the shape of the capsule 8. can do.

【００３５】ところで、本実施形態では、カプセル８の
材料をＡｌとしたが、カプセル８の材料はＡｌに限定す
るものではなく、線膨張率、押し出し加工時の変形抵抗
が熱電半導体１，２と同程度の材料であればよく、例え
ばＡｌ合金であってもよい。カプセル８の充填孔８ａに
各熱電半導体粉末１’，２’を充填した後は、図２
（ｂ）に示すように、脱気管９ａを備えたＡｌ製のカプ
セル蓋９とカプセル８とを溶接などにより接合すること
によって、押し出し加工用のビレット１０を作製する。
なお、粉末充填からの一連の作業は、各熱電半導体粉末
１’，２’の酸化による熱電特性劣化を防止するため
に、Ｎ2 ガスなどの不活性ガスの雰囲気中、Ｈ2 ガスな
どの酸化還元ガスの雰囲気中、あるいは真空中のいずれ
かで行うことが望ましい。その後、脱気管９ａを通して
ビレット１０の脱気処理（例えば、３００℃で２時間程
度の脱気処理）を行い、充填孔８ａの真空度が１．０×
１０-3Ｔｏｒｒ程度（０．１３３Ｐａ程度）になるよう
にする。In the present embodiment, the material of the capsule 8 is Al. However, the material of the capsule 8 is not limited to Al. It is sufficient if the material is of the same level, and for example, an Al alloy may be used. After filling the thermoelectric semiconductor powders 1 ′, 2 ′ into the filling holes 8a of the capsule 8, FIG.
As shown in (b), an aluminum billet 10 for extrusion is produced by joining the capsule lid 9 provided with the degassing pipe 9a and the capsule 8 by welding or the like.
A series of operations from the powder filling, the oxidation of the thermoelectric semiconductor powder 1 ', 2' in order to prevent the thermoelectric characteristic deterioration due to oxidation in an atmosphere of an inert gas such as N 2 gas, such as H 2 gas It is desirable to carry out the treatment in an atmosphere of a reducing gas or in a vacuum. After that, the billet 10 is deaerated (for example, at 300 ° C. for about 2 hours) through the deaeration tube 9a, and the degree of vacuum of the filling hole 8a is 1.0 ×
It is set to about 10 −3 Torr (about 0.133 Pa).

【００３６】そして、図２（ｃ）に示すように、ビレッ
ト１０を押し出し加工装置２０内のコンテナ２１にセッ
テイングする。ここに、セッテイングにあたっては、押
し出し加工性を良くするために、ビレット１０を３００
〜５００℃で２時間程度保持してビレット１０内部まで
充分に加熱することによりビレット１０に延性を付与し
て、押し出し加工時の変形抵抗を小さくすることが望ま
しい。Then, as shown in FIG. 2 (c), the billet 10 is set in a container 21 in the extrusion processing device 20. Here, in setting, the billet 10 was set to 300 to improve the extrudability.
It is desirable that the billet 10 be given ductility by being held at about 500 ° C. for about 2 hours and sufficiently heated to the inside of the billet 10 to reduce the deformation resistance during extrusion.

【００３７】次に、図２（ｄ）に示すように、ステム２
３を移動させてビレット１０を押圧することにより、押
し出し加工（静水圧押し出し加工）を行う。なお、図２
（ｃ），（ｄ）中の２２はダイを示し、２４は圧媒（例
えば、ひまし油やグリスなど）を示す。押し出しの条件
としては、例えば、押し出し時のビレット１０の温度は
３００〜５００℃、押し出し比は５〜５０、ステム速度
は１〜２０ｍｍ／ｓｅｃにすればよい。Next, as shown in FIG.
By extruding the billet 10 by moving 3, an extruding process (hydrostatic extruding process) is performed. Note that FIG.
In (c) and (d), 22 indicates a die, and 24 indicates a pressure medium (for example, castor oil or grease). As the conditions for the extrusion, for example, the temperature of the billet 10 at the time of extrusion may be 300 to 500 ° C., the extrusion ratio may be 5 to 50, and the stem speed may be 1 to 20 mm / sec.

【００３８】次に、図２（ｅ）に示すように、押し出し
加工装置２０から押し出されたビレット１０’（押し出
し部材）を焼結用の加熱炉３０の中に入れ、Ｎ2 ガスな
どの不活性ガスの雰囲気中、Ｈ2 ガスなどの酸化還元ガ
スの雰囲気中、あるいは真空中のいずれかで３５０℃〜
４５０℃、１０分〜１０時間の熱処理を行うことによ
り、ｐ形熱電半導体粉末１’及び熱電半導体粉末２’の
焼結を行う。そして、ｐ形熱電半導体粉末１’及び熱電
半導体粉末２’が焼結された後のビレット１０’を実施
形態１のブロック体４として以後実施形態１と同様の工
程により熱電変換モジュール１００を作製すればよい。Next, as shown in FIG. 2 (e), placed billet 10 extruded from the extrusion device 20 '(the pushing member) into the furnace 30 for sintering, not such as N 2 gas 350 ° C. in an atmosphere of an active gas, an atmosphere of a redox gas such as H 2 gas, or in a vacuum.
By performing heat treatment at 450 ° C. for 10 minutes to 10 hours, the p-type thermoelectric semiconductor powder 1 ′ and the thermoelectric semiconductor powder 2 ′ are sintered. Then, the billet 10 ′ after the p-type thermoelectric semiconductor powder 1 ′ and the thermoelectric semiconductor powder 2 ′ have been sintered is used as the block body 4 of the first embodiment, and thereafter, the thermoelectric conversion module 100 is manufactured by the same steps as in the first embodiment. I just need.

【００３９】ところで、本実施形態では、上述のように
導電性接合部材３として各熱電半導体１，２と同程度の
線膨張率及び変形抵抗を有する金属を用い、導電性接合
部材３と各熱電半導体１，２とを押し出し加工により接
合するので、一括して複数の導電性接合部材３と複数の
各導電形の熱電半導体１，２とを接合することができ
る。また、各熱電半導体１，２と導電性接合部材３との
線膨張率が同程度であることから、熱電変換モジュール
１００への通電時に電極６の接合界面における熱応力の
発生を抑制することができ、信頼性が向上する。また、
各熱電半導体１，２と導電性接合部材３との変形抵抗が
同程度であるから、押し出し加工時の形状制御が容易と
なる。また、導電性接合部材３と各熱電半導体１，２と
を押し出し加工により接合するので、一度に大量のブロ
ック体４を形成することが可能であり、生産性が向上す
る。ここで、導電性接合部材３として変形抵抗が小さい
金属を用いることにより、押し出し加工後の形状の制御
が容易になるとともに、押し出し速度を速くすることが
でき生産性が向上する。In the present embodiment, as described above, a metal having the same linear expansion coefficient and deformation resistance as the thermoelectric semiconductors 1 and 2 is used as the conductive bonding member 3, and the conductive bonding member 3 is Since the semiconductors 1 and 2 are joined by extrusion, the plurality of conductive joining members 3 and the plurality of thermoelectric semiconductors 1 and 2 of each conductivity type can be joined together. Further, since the thermal expansion coefficients of the thermoelectric semiconductors 1 and 2 and the conductive bonding member 3 are substantially the same, it is possible to suppress the generation of thermal stress at the bonding interface of the electrodes 6 when the thermoelectric conversion module 100 is energized. And reliability is improved. Also,
Since the deformation resistance of each of the thermoelectric semiconductors 1 and 2 and the conductive bonding member 3 is substantially the same, the shape control at the time of extrusion is facilitated. Further, since the conductive bonding member 3 and the thermoelectric semiconductors 1 and 2 are bonded by extrusion, a large number of block bodies 4 can be formed at once, and productivity is improved. Here, by using a metal having a small deformation resistance as the conductive bonding member 3, it is easy to control the shape after the extrusion, and the extrusion speed can be increased, thereby improving the productivity.

【００４０】ところで、本実施形態では、各熱電半導体
粉末１’，２’をカプセル８内の所定位置に充填した
後、押し出し加工を行うことにより導電性接合部材３と
各熱電半導体１，２とを接合するので、押し出し形状の
制御が容易になるとともに、押し出し加工により押し出
された熱電半導体１，２が多結晶になり、熱電半導体
１，２の機械的強度が向上する。また、押し出し加工前
の熱電半導体１，２を粉末としたことにより押し出し加
工時における熱電半導体１，２の変形抵抗が小さくなる
ので、押し出し速度が向上し生産性が向上する。In the present embodiment, after the thermoelectric semiconductor powders 1 ', 2' are filled in predetermined positions in the capsule 8, the conductive bonding member 3 and the thermoelectric semiconductors 1, 2 are extruded. Is joined, the extruded shape can be easily controlled, and the thermoelectric semiconductors 1 and 2 extruded by the extrusion process become polycrystalline, and the mechanical strength of the thermoelectric semiconductors 1 and 2 is improved. In addition, since the thermoelectric semiconductors 1 and 2 before extrusion are powdered, the deformation resistance of the thermoelectric semiconductors 1 and 2 during extrusion is reduced, so that the extrusion speed is improved and the productivity is improved.

【００４１】また、押し出し加工後に、押し出された押
し出し部材を焼結するので、熱電半導体１，２の機械的
強度の向上及び熱電半導体１，２と導電性接合部材３と
の接合強度の向上が図られる。 （実施形態３）本実施形態は、ｐ形熱電半導体粉末１’
及びｎ形熱電半導体粉末２’を予め所定の形状になるよ
う圧粉成形してｐ形熱電半導体圧粉体１”及びｎ形熱電
半導体圧粉体２”を作製した後に、ｐ形熱電半導体圧粉
体１”及びｎ形熱電半導体圧粉体２”をＡｌ製のカプセ
ル８に充填することを特徴とし、それ以外の方法につい
ては実施形態２と同様なので説明を省略する。Further, since the extruded extruded members are sintered after the extruding process, the mechanical strength of the thermoelectric semiconductors 1 and 2 and the joining strength between the thermoelectric semiconductors 1 and 2 and the conductive joining member 3 are improved. It is planned. (Embodiment 3) This embodiment is directed to a p-type thermoelectric semiconductor powder 1 '.
And n-type thermoelectric semiconductor powder 2 ′ are pre-compacted into a predetermined shape to produce p-type thermoelectric semiconductor compact 1 ″ and n-type thermoelectric semiconductor compact 2 ″. The method is characterized in that the powder 1 "and the n-type thermoelectric semiconductor compact 2" are filled in an Al capsule 8, and the other method is the same as that of the second embodiment, and the description is omitted.

【００４２】本実施形態では、図３（ａ）に示すように
一面開口した矩形箱状のゴム製容器４０の充填孔４０ａ
にｐ形熱電半導体粉末１’及びｎ形熱電半導体粉末２’
をそれぞれ別々に充填する。なお、本実施形態では、ゴ
ム製容器４０の充填孔４０ａは、短辺の長さを２．５２
ｍｍ、長辺の長さを２４．９ｍｍ、深さを２２５ｍｍと
してある。In this embodiment, as shown in FIG. 3A, a filling hole 40a of a rectangular box-shaped rubber
P-type thermoelectric semiconductor powder 1 'and n-type thermoelectric semiconductor powder 2'
Are charged separately. In the present embodiment, the filling hole 40a of the rubber container 40 has a short side length of 2.52.
mm, the length of the long side is 24.9 mm, and the depth is 225 mm.

【００４３】複数のゴム製容器４０に熱電半導体粉末
１’，２’を別々に充填した後は、図３（ｂ）に示すよ
うに、ゴム製容器４０にゴム製蓋４０ｂを取り付けて気
密シールしてＣＩＰ（冷間静水圧プレス）用の炉５０内
の圧力媒体中に投入し、ゴム製容器４０とゴム製蓋４０
ｂとで構成される成形型の外表面に法線方向の均一な圧
力を加える（例えば、１０〜１００ｋｇ／ｍｍ2 の加圧
力で等方的にＣＩＰを行う）。その後、図３（ｃ）に示
すように、上記成形型から離型したｐ形熱電半導体圧粉
体１”及びｎ形熱電半導体圧粉体２”をＡｌ製のカプセ
ル８の充填孔８ａに挿入し、実施形態２と同様に、脱気
管９ａを備えたＡｌ製のカプセル蓋９とカプセル８とを
溶接などにより接合することによって、押し出し加工用
のビレット１０を作製する。その後の製造工程は実施形
態２と同様である。After separately filling the plurality of rubber containers 40 with the thermoelectric semiconductor powders 1 'and 2', as shown in FIG. 3 (b), a rubber lid 40b is attached to the rubber containers 40 to form an airtight seal. Into a pressure medium in a furnace 50 for a CIP (cold isostatic press), and a rubber container 40 and a rubber lid 40.
b. A uniform pressure in the normal direction is applied to the outer surface of the mold composed of b) (for example, CIP isotropically performed at a pressure of 10 to 100 kg / mm 2 ). Thereafter, as shown in FIG. 3C, the p-type thermoelectric semiconductor compact 1 "and the n-type thermoelectric semiconductor compact 2" released from the mold are inserted into the filling hole 8a of the Al capsule 8. Then, similarly to the second embodiment, a billet 10 for extruding is manufactured by joining the capsule lid 9 provided with the degassing pipe 9a and the capsule 8 made of Al by welding or the like. Subsequent manufacturing steps are the same as in the second embodiment.

【００４４】本実施形態では、ｐ形熱電半導体圧粉体
１”及びｎ形熱電半導体圧粉体２”をＡｌ製のカプセル
８の充填孔８ａに充填（挿入）するので、実施形態２の
ようにカプセル８の充填孔８ａに熱電半導体粉末１’，
２’を充填する場合に比べて熱電半導体の取扱いが容易
になるとともに、熱電半導体が酸化しにくくなる。 （実施形態４）本実施形態は、ｐ形熱電半導体１、ｎ形
熱電半導体２、導電性接合部材３を一体化したブロック
体４の形成方法に特徴があり、ｐ形熱電半導体粉末
１’、ｎ形熱電半導体粉末２’を後述のように加圧焼結
することによりブロック体４を形成している。なお、ブ
ロック体４を形成した後の製造方法は実施形態１と同様
であるから説明は省略する。In the present embodiment, the p-type thermoelectric semiconductor compact 1 "and the n-type thermoelectric semiconductor compact 2" are filled (inserted) into the filling hole 8a of the Al capsule 8, so that as in the second embodiment. The thermoelectric semiconductor powder 1 'in the filling hole 8a of the capsule 8,
The handling of the thermoelectric semiconductor is easier than in the case where 2 ′ is filled, and the thermoelectric semiconductor is less likely to be oxidized. (Embodiment 4) This embodiment is characterized by a method of forming a block 4 in which a p-type thermoelectric semiconductor 1, an n-type thermoelectric semiconductor 2, and a conductive bonding member 3 are integrated, and a p-type thermoelectric semiconductor powder 1 ', The block body 4 is formed by sintering the n-type thermoelectric semiconductor powder 2 'under pressure as described later. The manufacturing method after the formation of the block body 4 is the same as that of the first embodiment, and thus the description is omitted.

【００４５】本実施形態では、図４（ａ）に示すよう
に、上面に矩形状の充填孔７１（凹所）を有する金型７
０の上記充填孔７１に、所定量のｐ形熱電半導体粉末
１’もしくはｎ形熱電半導体粉末２’を粉末充填用容器
７２の先端部７２ａを通して充填する。なお、本実施形
態では、上記充填孔７１の寸法は、短辺を２．１ｍｍ、
長辺を５．１ｍｍ、深さを２．８ｍｍとしてある。In this embodiment, as shown in FIG. 4A, a mold 7 having a rectangular filling hole 71 (concave portion) on the upper surface.
A predetermined amount of the p-type thermoelectric semiconductor powder 1 ′ or the n-type thermoelectric semiconductor powder 2 ′ is filled in the filling hole 71 through the tip 72 a of the powder filling container 72. In addition, in this embodiment, the dimension of the said filling hole 71 is 2.1 mm in a short side,
The long side is 5.1 mm and the depth is 2.8 mm.

【００４６】金型７０の充填孔７１にｐ形熱電半導体粉
末１’もしくはｎ形熱電半導体粉末２’を充填した後
は、図４（ｂ）に示すように予備圧粉用のパンチ７３に
よりｐ形熱電半導体粉末１’もしくはｎ形熱電半導体粉
末２’を加圧することによって予備圧粉を行い矩形板状
のｐ形熱電半導体圧粉体１”及び矩形板状のｎ形熱電半
導体圧粉体２”を形成する。ここで、上記パンチ７３の
先端部７３ａの断面形状は充填孔７１の断面形状と略等
しくかつ圧粉の作業をスムーズに行えるように０．２ｍ
ｍ程度のクリアランスを設けてある。ｐ形熱電半導体圧
粉体１”及びｎ形熱電半導体圧粉体２”を形成した後
は、図４（ｃ）に示すように、ホットプレス装置８０の
ベース部８１上に、ｐ形熱電半導体圧粉体１”とｎ形熱
電半導体圧粉体２”とを導電性接合部材３を介して交互
に積層する。つまり、ホットプレス装置８０のベース部
８１上には、導電性接合部材３、ｐ形熱電半導体圧粉体
１”、導電性接合部材３、ｎ形熱電半導体圧粉体２”、
導電性接合部材３の順に積層されることになる（以後、
この積層したものを積層体と称す）。なお、本実施形態
では、導電性接合部材３の外形寸法は、短辺の長さを
２．１ｍｍ、長辺の長さを５．１ｍｍ、厚さを０．２ｍ
ｍとしてあり、熱電半導体圧粉体１”，２”と導電性接
合部材３とは互いに接触する面を略同じ外形寸法に形成
してある。After the filling hole 71 of the mold 70 is filled with the p-type thermoelectric semiconductor powder 1 'or the n-type thermoelectric semiconductor powder 2', the p-type thermoelectric semiconductor powder 2 'is pressed by the pre-compacting punch 73 as shown in FIG. The pre-compacting is performed by pressing the thermoelectric semiconductor powder 1 'or n-type thermoelectric semiconductor powder 2', and the rectangular plate-shaped p-type thermoelectric semiconductor compact 1 "and the rectangular plate-shaped n-type thermoelectric semiconductor compact 2 Is formed. Here, the cross-sectional shape of the tip portion 73a of the punch 73 is substantially equal to the cross-sectional shape of the filling hole 71, and is 0.2 m so that the work of compacting can be performed smoothly.
A clearance of about m is provided. After forming the p-type thermoelectric semiconductor compacts 1 ″ and the n-type thermoelectric semiconductor compacts 2 ″, as shown in FIG. The green compacts 1 ″ and the n-type thermoelectric semiconductor green compacts 2 ″ are alternately laminated via the conductive bonding member 3. That is, on the base portion 81 of the hot press device 80, the conductive bonding member 3, the p-type thermoelectric semiconductor compact 1 ", the conductive bonding member 3, the n-type thermoelectric semiconductor compact 2",
The conductive bonding members 3 are laminated in this order (hereinafter, referred to as “conductive bonding members 3”)
This laminate is referred to as a laminate). In the present embodiment, the outer dimensions of the conductive bonding member 3 are such that the length of the short side is 2.1 mm, the length of the long side is 5.1 mm, and the thickness is 0.2 m.
m, and the surfaces of the thermoelectric semiconductor compacts 1 ″, 2 ″ and the conductive bonding member 3 that are in contact with each other are formed to have substantially the same external dimensions.

【００４７】ホットプレス装置８０のベース部８１上に
ｐ形熱電半導体圧粉体１”、導電性接合部材３、ｎ形熱
電半導体圧粉体２”を積層した後は、ホットプレス装置
８０の備えているヒータ８４，８５により雰囲気温度を
３５０℃〜４５０℃程度に加熱した状態で、図４（ｄ）
に示すように、ホットプレス用のパンチ８３を下降させ
て上記積層体を加圧焼結し、冷却後に取り出すことによ
り図４（ｅ）に示すようなブロック体４が得られる。な
お、ホットプレス装置による成形条件としては、例えば
成形圧を３０ｋｇ／ｍｍ2 〜１００ｋｇ／ｍｍ2 、成形
時間を１０分〜１０時間とし、Ｎ2 ガス等の不活性ガス
雰囲気中、Ｈ2 ガスなどの酸化還元ガス雰囲気中、ある
いは真空中のいずれかにて加圧することが望ましい。After laminating the p-type thermoelectric semiconductor compact 1 ”, the conductive bonding member 3 and the n-type thermoelectric semiconductor compact 2” on the base 81 of the hot press 80, the hot press 80 is provided. FIG. 4D shows a state in which the ambient temperature is heated to about 350 ° C. to 450 ° C. by the heaters 84 and 85 which are provided.
As shown in FIG. 4 (b), the stacked body is press-sintered by lowering the punch 83 for hot press, taken out after cooling, and the block body 4 as shown in FIG. 4 (e) is obtained. The hot press apparatus may be formed under conditions of, for example, a molding pressure of 30 kg / mm 2 to 100 kg / mm 2 , a molding time of 10 minutes to 10 hours, an inert gas atmosphere such as N 2 gas, H 2 gas, or the like. It is desirable to pressurize in either a redox gas atmosphere or vacuum.

【００４８】本実施形態では、各熱電半導体１，２の加
圧と焼結とを同時に行うので、ｐ形熱電半導体及びｎ形
熱電半導体の機械的強度が向上してブロック体４の強度
が向上する。また、各熱電半導体１，２の加圧と焼結と
を同時に行うことにより、各熱電半導体１，２の結晶面
が一軸に配向するので、各熱電半導体１，２の熱電特性
が向上する。なお、導電性接合部材３としては各熱電半
導体１，２と同程度の弾性率を有する材料を用いればよ
く、例えばＡｌやＡｌ合金を用いればよい。In the present embodiment, since the pressing and sintering of the thermoelectric semiconductors 1 and 2 are simultaneously performed, the mechanical strength of the p-type thermoelectric semiconductor and the n-type thermoelectric semiconductor is improved, and the strength of the block body 4 is improved. I do. In addition, by simultaneously pressing and sintering each of the thermoelectric semiconductors 1 and 2, the crystal plane of each of the thermoelectric semiconductors 1 and 2 is uniaxially oriented, so that the thermoelectric characteristics of each of the thermoelectric semiconductors 1 and 2 are improved. The conductive bonding member 3 may be made of a material having the same elastic modulus as the thermoelectric semiconductors 1 and 2, for example, Al or an Al alloy.

【００４９】（実施形態５）ところで、実施形態４では
予備圧粉されたｐ形熱電半導体圧粉体１”及びｎ形熱電
半導体圧粉体２”をホットプレス装置８０により加圧焼
結していたが、本実施形態では、熱間静水圧プレス（Ｈ
ＩＰ）によりｐ形熱電半導体圧粉体１”及びｎ形熱電半
導体圧粉体２”を加圧焼結する点を特徴とし、それ以外
の製造方法は実施形態４と同様なので説明を省略する。(Embodiment 5) By the way, in Embodiment 4, the p-type thermoelectric semiconductor compact 1 "and the n-type thermoelectric semiconductor compact 2" which have been pre-compacted are pressure-sintered by the hot press device 80. However, in this embodiment, the hot isostatic press (H
The method is characterized in that the p-type thermoelectric semiconductor compact 1 "and the n-type thermoelectric semiconductor compact 2" are pressed and sintered by IP).

【００５０】本実施形態では、まず、図５（ａ）に示す
ように、予備圧粉されたｐ形熱電半導体圧粉体１”と、
ｎ形熱電半導体圧粉体２”と、導電性接合部材３とを、
上面開口した直方体状の金属製カプセル１５の収納室１
５ａに実施形態４と同様の順番で積層し（つまり、導電
性接合部材３、ｐ形熱電半導体圧粉体１”、導電性接合
部材３、ｎ形熱電半導体圧粉体２”、導電性接合部材
３、ｐ形熱電半導体圧粉体１”、・・・の順に積層
し）、金属製カプセル１５に金属製の蓋１５ｂを取着す
る。その後、３００℃で２時間の加熱脱気処理を行うこ
とにより、ｐ形熱電半導体圧粉体１”及びｎ形熱電半導
体圧粉体２”それぞれの表面に吸着している吸着ガスを
除去し、金属製カプセル１５内の真空度が１．０×１０
-3Ｔｏｒｒ程度（０．１３３Ｐａ程度）になるようにす
る。In this embodiment, first, as shown in FIG. 5 (a), a p-type thermoelectric semiconductor compact 1 "which has been pre-compacted is provided.
The n-type thermoelectric semiconductor compact 2 ″ and the conductive bonding member 3 are
Storage room 1 for rectangular parallelepiped metal capsule 15 with open top
5a are laminated in the same order as in the fourth embodiment (that is, the conductive bonding member 3, the p-type thermoelectric semiconductor green compact 1 ″, the conductive bonding member 3, the n-type thermoelectric semiconductor green compact 2 ″, the conductive bonding The member 3, the p-type thermoelectric semiconductor compact 1 '',... Are laminated in this order), and a metal lid 15b is attached to the metal capsule 15. Then, a heat deaeration treatment is performed at 300 ° C. for 2 hours. By doing so, the adsorbed gas adsorbed on the surface of each of the p-type thermoelectric semiconductor compact 1 "and the n-type thermoelectric semiconductor compact 2" is removed, and the degree of vacuum in the metal capsule 15 becomes 1.0 × 10
-3 Torr (about 0.133 Pa).

【００５１】次に、図５（ｂ）に示すように、金属製カ
プセル１５を圧力容器（ＨＩＰ用炉）内の所定の位置に
設置し、アルゴンガスや窒素ガスを圧力媒体として、高
温高圧で加圧焼結を行う。なお、この時の雰囲気温度は
３５０℃〜４５０℃、成形圧は３０ｋｇ／ｍｍ2 〜１０
０ｋｇ／ｍｍ2 、成形時間は１０分〜１０時間とする。Next, as shown in FIG. 5 (b), a metal capsule 15 is set at a predetermined position in a pressure vessel (HIP furnace), and is heated at a high temperature and a high pressure using argon gas or nitrogen gas as a pressure medium. Pressure sintering is performed. At this time, the ambient temperature was 350 ° C. to 450 ° C., and the molding pressure was 30 kg / mm 2 to 10
0 kg / mm 2 , and the molding time is 10 minutes to 10 hours.

【００５２】本実施形態では、加圧と焼結とを同時に行
っているので、焼結中のネック（ネック形成）の再結合
が促進されるから各熱電半導体１，２の機械的強度が向
上し、結果として熱電変換モジュール１００の機械的強
度が向上する。 （実施形態６）本実施形態は、ｐ形熱電半導体圧粉体
１”及びｎ形熱電半導体圧粉体２”を導電性接合部材
３’を介して交互に積層し、押し出し加工を行う点に特
徴がある。なお、押し出し加工によってブロック体４’
を形成した後の製造方法は実施形態１と同様であるから
説明を省略する。In this embodiment, since the pressurization and the sintering are performed simultaneously, the recombination of the neck (formation of the neck) during the sintering is promoted, so that the mechanical strength of each of the thermoelectric semiconductors 1 and 2 is improved. As a result, the mechanical strength of the thermoelectric conversion module 100 is improved. (Embodiment 6) The present embodiment is characterized in that p-type thermoelectric semiconductor compacts 1 "and n-type thermoelectric semiconductor compacts 2" are alternately laminated via a conductive bonding member 3 'and extruded. There are features. In addition, the block body 4 ′ is extruded.
Since the manufacturing method after forming is the same as in the first embodiment, the description is omitted.

【００５３】本実施形態では、図６（ａ）に示すｐ形熱
電半導体圧粉体１”（ｎ形熱電半導体圧粉体２”）の全
面に、プラズ溶射によりＳｎ膜４００を形成する（図６
（ｂ）参照）。ここに、Ｓｎ膜４００は導電性中間部材
を構成する。なお、本実施形態では、Ｓｎ膜４００の膜
厚は押し出し比が２０の場合には５μｍ以上必要であ
り、押し出し比が大きくなるにつれて押し出し後のＳｎ
膜４００’の膜厚が薄くなるので、押し出し比に応じて
Ｓｎ膜４００の膜厚を変化させることが望ましい。ま
た、押し出し加工後の加熱処理の温度、つまり、焼結温
度が高い場合にはＳｎの拡散量が多くなるので、焼結温
度が高いほどＳｎ膜４００の膜厚を厚くすることが望ま
しい。以上の点を考慮して本実施形態では、Ｓｎ膜４０
０の膜厚を１０μｍ〜２００μｍとしてある。以下、Ｓ
ｎ膜４００の形成方法について説明する。In this embodiment, an Sn film 400 is formed on the entire surface of the p-type thermoelectric semiconductor compact 1 "(n-type thermoelectric semiconductor compact 2") shown in FIG. 6
(B)). Here, the Sn film 400 forms a conductive intermediate member. In this embodiment, when the extrusion ratio is 20, the thickness of the Sn film 400 needs to be 5 μm or more, and as the extrusion ratio increases, the thickness of the Sn film after extrusion increases.
Since the thickness of the film 400 ′ becomes thin, it is desirable to change the thickness of the Sn film 400 according to the extrusion ratio. Further, when the temperature of the heat treatment after the extruding process, that is, the sintering temperature is high, the amount of Sn diffusion increases, so that the higher the sintering temperature, the thicker the Sn film 400 is desirably. In the present embodiment, in consideration of the above points, the Sn film 40
The film thickness of 0 is 10 μm to 200 μm. Hereinafter, S
A method for forming the n film 400 will be described.

【００５４】まず、ｐ形熱電半導体圧粉体１”（ｎ形熱
電半導体圧粉体２”）の表面をサンドペーパ（例えば、
ＦＵＪＩＳＴＡＲ４００番相当）で研磨した後に、エタ
ノール中にて超音波洗浄し（例えば、２分程度）、乾燥
後に、ｐ形熱電半導体圧粉体１”（ｎ形熱電半導体圧粉
体２”）の全面をプラズマエッチング（エッチング条件
としては、例えば、ＲＦパワー：３００Ｗ、エッチング
ガス：Ａｒ、エッチング圧力：６．６Ｐａ、エッチング
時間：１分）することにより清浄化し、該清浄化された
表面に、減圧プラズマ溶射（アーク放電電力：５ｋＷ、
圧力：１ｋＰａ、雰囲気ガス：Ａｒ）によってＳｎ膜４
００を形成する。First, the surface of the p-type thermoelectric semiconductor compact 1 ″ (n-type thermoelectric semiconductor compact 2 ″) is sandpapered (for example,
After polishing with FUJISTAR No. 400), ultrasonic cleaning in ethanol (for example, about 2 minutes), drying, and the entire surface of the p-type thermoelectric semiconductor compact 1 "(n-type thermoelectric semiconductor compact 2") By plasma etching (as etching conditions, for example, RF power: 300 W, etching gas: Ar, etching pressure: 6.6 Pa, etching time: 1 minute), and the cleaned surface is subjected to reduced pressure plasma. Thermal spraying (arc discharge power: 5 kW,
Pressure: 1 kPa, atmosphere gas: Ar) Sn film 4
00 is formed.

【００５５】Ｓｎ膜４００を形成した後は、Ｓｎ膜４０
０表面に減圧プラズマ溶射（アーク放電電力：５ｋＷ、
圧力：１ｋＰａ、雰囲気ガス：Ａｒ）によりＭｏ膜４０
１を形成する（図６（ｃ）参照）。なお、本実施形態で
は、Ｍｏ膜４０１の膜厚を３μｍ以上にしてあるが、Ｍ
ｏ膜４０１の膜厚の設定については、Ｓｎ膜４００の膜
厚を決める場合と同様の配慮が必要である。なお、減圧
プラズマ溶射において雰囲気ガスとしてＡｒを使用する
ことにより酸化を防止することがき、良好な接合を得る
ことができる。また、圧力が低いほどプラズマジェット
の流速や高温領域が増大して密着力が向上し、圧力とし
ては２０ｋＰａ以下にすることが望ましい。After forming the Sn film 400, the Sn film 40
0 low pressure plasma spraying (arc discharge power: 5 kW,
Pressure: 1 kPa, atmosphere gas: Ar) Mo film 40
1 (see FIG. 6C). In this embodiment, the thickness of the Mo film 401 is set to 3 μm or more.
Regarding the setting of the film thickness of the o film 401, the same consideration as in the case of determining the film thickness of the Sn film 400 is necessary. In addition, oxidation can be prevented by using Ar as an atmosphere gas in the reduced pressure plasma spraying, and a good junction can be obtained. Further, as the pressure is lower, the flow velocity of the plasma jet and the high-temperature region are increased to improve the adhesion, and the pressure is desirably 20 kPa or less.

【００５６】また、図６（ｄ）に示す例えばアルミニウ
ム板よりなる導電性接合部材３’の表面を粗面化するた
めに該表面を機械的に切削することにより、導電性接合
部材３’の表面に凹凸を形成する（図６（ｅ）参照）。
その後、導電性接合部材３’の表面にスパッタリングに
よりＭｏ膜４１１を形成する。なお、本実施形態では、
Ｍｏ膜４１１の膜厚は０．５μｍ以上としている。Further, by mechanically cutting the surface of the conductive joining member 3 ′ made of, for example, an aluminum plate as shown in FIG. Irregularities are formed on the surface (see FIG. 6E).
Thereafter, a Mo film 411 is formed on the surface of the conductive bonding member 3 ′ by sputtering. In the present embodiment,
The thickness of the Mo film 411 is 0.5 μm or more.

【００５７】そして、図６（ｇ）に示すようにＳｎ膜４
００及びＭｏ膜４０１が形成された熱電半導体圧粉体
１”，２”をＭｏ膜４１１が形成された導電性接合部材
３’を介して交互に積層し、押し出し加工を行うことに
より図６（ｈ）に示すようなブロック体４’が得られ
る。ここに、Ｍｏ膜４０１，４１１は拡散防止層を構成
する。Then, as shown in FIG.
6 are formed by alternately laminating the thermoelectric semiconductor compacts 1 ″ and 2 ″ on which the Mo film 401 is formed via the conductive bonding member 3 ′ on which the Mo film 411 is formed, and performing extrusion. The block body 4 'as shown in h) is obtained. Here, the Mo films 401 and 411 constitute a diffusion preventing layer.

【００５８】本実施形態の接合法によれば、各熱電半導
体１，２の構成元素の化学族と、導電性中間部材（拡散
材）であるＳｎの化学族とが近く、各熱電半導体１，２
中にＳｎが拡散しやすくので、Ｓｎ膜４００と各熱電半
導体１，２との接合強度が向上する。ここに、熱電半導
体１，２中にＳｎが拡散されたことによる熱電半導体
１，２の性能劣化や経時劣化は小さく、熱電変換モジュ
ールの熱電性能の信頼性を損なうことはない。According to the bonding method of this embodiment, the chemical group of the constituent elements of each of the thermoelectric semiconductors 1 and 2 and the chemical group of Sn as the conductive intermediate member (diffusion material) are close to each other. 2
Since Sn is easily diffused therein, the bonding strength between the Sn film 400 and each of the thermoelectric semiconductors 1 and 2 is improved. Here, the performance deterioration and the deterioration over time of the thermoelectric semiconductors 1 and 2 due to the diffusion of Sn into the thermoelectric semiconductors 1 and 2 are small, and the reliability of the thermoelectric performance of the thermoelectric conversion module is not impaired.

【００５９】また、他の導電性中間部材であるＭｏ膜４
０１，４１１は、拡散防止効果が高く接合部材としても
有効なので、Ｍｏ膜４０１，４１１を通るような相互拡
散が防止され、相互拡散による接合強度の低下や熱電半
導体１，２の熱電性能の経時劣化が抑制される。また、
本実施形態では、ｐ形熱電半導体圧粉体１”，ｎ形熱電
半導体圧粉体２”，導電性接合部材３’それぞれの表面
を粗面化することにより接合面の面積を増大させている
ので、接合強度が向上する。しかも、導電性中間部材で
あるＭｏ膜４１１を導電性接合部材３の表面にスパッタ
リングにより形成して密着させているので、導電性接合
部材３とＭｏ膜４１１の接合強度が高められる。なお、
Ｍｏ膜４１１などの導電性中間部材を導電性接合部材
３’の表面に形成する方法としてはスパッタリングに限
定するものではなく、メッキやペースト塗布などの方法
を用いてもよい。The Mo film 4 which is another conductive intermediate member
Nos. 01 and 411 have a high diffusion prevention effect and are also effective as a bonding member. Therefore, mutual diffusion such as passing through the Mo films 401 and 411 is prevented, so that the bonding strength is reduced due to the mutual diffusion and the thermoelectric performance of the thermoelectric semiconductors 1 and 2 with time. Deterioration is suppressed. Also,
In the present embodiment, the area of the bonding surface is increased by roughening the surface of each of the p-type thermoelectric semiconductor green compact 1 ″, the n-type thermoelectric semiconductor green compact 2 ″, and the conductive bonding member 3 ′. Therefore, the joining strength is improved. Moreover, since the Mo film 411, which is a conductive intermediate member, is formed on the surface of the conductive bonding member 3 by sputtering and adheres to the surface, the bonding strength between the conductive bonding member 3 and the Mo film 411 is increased. In addition,
The method for forming the conductive intermediate member such as the Mo film 411 on the surface of the conductive bonding member 3 'is not limited to sputtering, but may be a method such as plating or paste application.

【００６０】ところで、本実施形態では、導電性中間部
材としてＳｎ膜４００を用いているが、導電性中間部材
はＳｎ膜に限定するものではなく、Ｂｉ膜やＳｂ膜など
を用いてもよい。また、拡散防止層は、Ｍｏ膜に限定す
るものではなく、Ｎｉ膜やＴｉ膜やＡｌ膜などを用いて
もよい。 （実施形態７）本実施形態では、実施形態６で述べたＭ
ｏ膜４０１が形成された熱電半導体１、２とＭｏ膜が形
成された導電性接合部材３’との間に、図７に示すよう
にＣｕ箔もしくはＣｕ板よりなる延性の高い導電性金属
部材４０２（導電性中間部材）を介在させていることを
特徴とする。本実施形態では、導電性金属部材４０２を
介在させることにより、実施形態６の製造方法に比べて
押し出し加工時（加圧接合時）に接合界面で発生する応
力を緩和することができ、応力が緩和されることによ
り、押し出し加工時の形状制御性が向上するので、押し
出し加工により形成されたブロック体４をスライスして
小ブロック体５を形成する工程の歩留りの向上を図るこ
とができる。なお、本実施形態では、導電性金属部材４
０２の厚さは１０μｍ〜２００μｍとしてある。また、
導電性金属部材４０２はＣｕに限定するものではなく、
Ａｇ，Ａｕ，Ｐｂ，Ａｌなどを用いてもよい。In the present embodiment, the Sn film 400 is used as the conductive intermediate member. However, the conductive intermediate member is not limited to the Sn film, but may be a Bi film, an Sb film, or the like. Further, the diffusion prevention layer is not limited to the Mo film, but may be a Ni film, a Ti film, an Al film, or the like. (Embodiment 7) In the present embodiment, the M
As shown in FIG. 7, a highly ductile conductive metal member made of a Cu foil or a Cu plate is provided between the thermoelectric semiconductors 1 and 2 on which the o film 401 is formed and the conductive bonding member 3 'on which the Mo film is formed. 402 (conductive intermediate member) is interposed. In the present embodiment, by interposing the conductive metal member 402, the stress generated at the bonding interface during extrusion (press bonding) can be reduced as compared with the manufacturing method of the sixth embodiment. By relaxing the shape, the shape controllability at the time of the extrusion is improved, so that the yield of the process of slicing the block 4 formed by the extrusion to form the small block 5 can be improved. In this embodiment, the conductive metal member 4
02 has a thickness of 10 μm to 200 μm. Also,
The conductive metal member 402 is not limited to Cu,
Ag, Au, Pb, Al or the like may be used.

【００６１】（実施形態８）ところで、熱電半導体１，
２が粉末（ｐ形熱電半導体粉末１’，ｎ形熱電半導体粉
末２’）である場合、実施形態６の製造方法を適用する
ことができないので、本実施形態では、図８（ａ）に示
すような導電性中間部材であるＳｎよりなる直方体状の
容器５５にｐ形熱電半導体粉末１’（ｎ形熱電半導体粉
末２’）を充填し、図８（ｂ）に示すように容器５５に
導電性中間層材であるＳｎ製の蓋５６を取着し、図８
（ｃ）に示すように、ｐ形熱電半導体粉末１’が充填さ
れた容器５５と、ｎ形熱電半導体粉末２’が充填された
容器５５とを導電性接合部材３’を介して交互に積層し
た後に、押し出し加工を行う。なお、本実施形態では、
容器５５の外形は、短辺の長さを２．２３ｍｍ、長辺の
長さを１１．１５ｍｍ、高さを２００ｍｍとし、容器５
５の各周壁の厚さを１００μｍとしてある。(Embodiment 8) By the way, the thermoelectric semiconductors 1,
In the case where 2 is a powder (p-type thermoelectric semiconductor powder 1 ′, n-type thermoelectric semiconductor powder 2 ′), the manufacturing method of Embodiment 6 cannot be applied. A p-type thermoelectric semiconductor powder 1 ′ (n-type thermoelectric semiconductor powder 2 ′) is filled in a rectangular parallelepiped container 55 made of Sn as such a conductive intermediate member, and the container 55 is electrically conductive as shown in FIG. A lid 56 made of Sn, which is a conductive intermediate layer material, is attached, and FIG.
As shown in (c), the container 55 filled with the p-type thermoelectric semiconductor powder 1 'and the container 55 filled with the n-type thermoelectric semiconductor powder 2' are alternately laminated via the conductive bonding member 3 '. After that, extrusion is performed. In the present embodiment,
The outer shape of the container 55 has a short side length of 2.23 mm, a long side length of 11.15 mm, and a height of 200 mm.
The thickness of each peripheral wall of No. 5 is 100 μm.

【００６２】本実施形態では、導電性中間部材を容器状
にしているので、導電性中間部材の厚さを均一にするこ
とができるという利点がある。また、導電性中間部材を
容器状にして各熱電半導体粉末１’，２’を充填するの
で、製造工程の省力化を図ることができる。 （実施形態９）本実施形態は、実施形態１で説明した小
ブロック体５を形成した後、小ブロック体５から導電性
接合部材３の一部を除去することにより電極６を形成す
る工程で、ダイシングソー７を用いる代わりに、レーザ
ＬＡ（例えば、エキシマレーザ）を用いる点に特徴があ
る。以下、図９に基づいて説明するが、同図（ａ）
〜（）の左側の図は小ブロック体５（もしくは熱電変換
モジュール１００）の正面図を示し、右側の図は上記左
側の部材の側面図を示す。In this embodiment, since the conductive intermediate member is formed in a container shape, there is an advantage that the thickness of the conductive intermediate member can be made uniform. In addition, since the conductive intermediate member is formed into a container and filled with the thermoelectric semiconductor powders 1 ′ and 2 ′, it is possible to save labor in the manufacturing process. (Embodiment 9) This embodiment is a process of forming an electrode 6 by forming a small block body 5 described in Embodiment 1 and then removing a part of the conductive bonding member 3 from the small block body 5. It is characterized in that a laser LA (for example, an excimer laser) is used instead of using the dicing saw 7. Hereinafter, description will be made with reference to FIG.
() Shows a front view of the small block body 5 (or the thermoelectric conversion module 100), and a right view shows a side view of the left member.

【００６３】図９（ａ）に示すような小ブロック体５の
導電性接合部材３の一部を除去して図９（ｄ）に示すよ
うな複数の電極６を形成するには、まず図９（ｂ）に示
すように小ブロック体５の上面（図９（ｂ）の上側）か
ら下方に向かって（矢印Ａの向きに）レーザ光ＬＢを走
査することにより導電性接合部材３を１つおきにその一
部を除去して電極６を形成し、次に、図９（ｃ）に示す
ように小ブロック体５の下面（図９（ｃ）の下側）から
上方に向かって（矢印Ｂの向きに）レーザ光ＬＢを走査
することにより導電性接合部材３を１つおきにその一部
を除去して電極６を形成する。なお、導電性接合部材３
は、小ブロック体５の上面からもしくは下面からどちら
か一方からしか除去しない。To form a plurality of electrodes 6 as shown in FIG. 9D by removing a part of the conductive bonding member 3 of the small block body 5 as shown in FIG. As shown in FIG. 9B, the laser beam LB is scanned downward (in the direction of arrow A) from the upper surface of the small block body 5 (the upper side in FIG. An electrode 6 is formed by removing part of every other electrode, and then, as shown in FIG. 9C, the small block 5 is directed upward from the lower surface (the lower side of FIG. 9C) ( By scanning the laser beam LB (in the direction of arrow B), every other conductive bonding member 3 is partially removed to form the electrode 6. In addition, the conductive bonding member 3
Is removed only from either the upper surface or the lower surface of the small block body 5.

【００６４】なお、レーザ光ＬＢを１回走査しただけで
導電性接合部材３を所望の量だけ除去できない場合に
は、レーザ光ＬＢを適宜往復走査すればよい。本実施形
態では、電極６を形成する工程において、ダイシングソ
ー７を用いる場合に比べて微細加工が可能になるととも
に、ダイシングソー７で加工できないような加工を施す
ことも可能となる。If the desired amount of the conductive bonding member 3 cannot be removed by scanning the laser beam LB once, the laser beam LB may be scanned back and forth as appropriate. In the present embodiment, in the step of forming the electrode 6, fine processing can be performed as compared with the case of using the dicing saw 7, and processing that cannot be performed by the dicing saw 7 can be performed.

【００６５】（実施形態１０）本実施形態は、実施形態
１で説明した小ブロック体５を形成した後、小ブロック
体５から導電性接合部材３の一部を除去することにより
電極６を形成する工程で、ダイシングソー７を用いる代
わりに、サンドブラストにより導電性接合部材３の一部
を除去する点に特徴がある。(Embodiment 10) In this embodiment, after forming the small block body 5 described in the first embodiment, the electrode 6 is formed by removing a part of the conductive bonding member 3 from the small block body 5. In this step, a part of the conductive bonding member 3 is removed by sandblasting instead of using the dicing saw 7.

【００６６】本実施形態では、 図１０（ａ）に示すよ
うな小ブロック体５の導電性接合部材３の一部を除去し
て図１０（ｄ）に示すような複数の電極６を形成するに
は、図１０（ａ）に示すような複数の電極６を形成する
には、まず図１０（ｂ）に示すように小ブロック体５の
正面（図１０（ｂ）の紙面表側）及び背面（図１０
（ｂ）の紙面裏側）に、除去部以外を覆うような（除去
部に対応する部位に開口部５８ａを有する）金属製マス
ク５８を設け、サンドブラストを行うことにより各導電
性接合部材３の一部を除去して電極６を形成する。その
後、金属製マスク５８を取り除くことにより、図１０
（ｃ）に示すような所望の電極６を有する熱電変換モジ
ュール１００が得られる。In this embodiment, a plurality of electrodes 6 as shown in FIG. 10D are formed by removing a part of the conductive bonding member 3 of the small block body 5 as shown in FIG. 10A. In order to form a plurality of electrodes 6 as shown in FIG. 10 (a), first, as shown in FIG. 10 (b), the front (the front side in FIG. 10 (b)) and the back of the small block body 5 are formed. (FIG. 10
A metal mask 58 (having an opening 58a at a portion corresponding to the removed portion) is provided on the back side of the drawing of FIG. The electrode 6 is formed by removing the portion. After that, the metal mask 58 is removed to obtain FIG.
The thermoelectric conversion module 100 having the desired electrodes 6 as shown in FIG.

【００６７】本実施形態では、小ブロック体５を構成す
る導電性接合部材３を広い範囲で一括して加工すること
が可能となるので、電極６を形成する工程の時間を短縮
することができ、生産性が向上する。 （実施形態１１）本実施形態は、ｐ形熱電半導体１及び
ｎ形熱電半導体２の結晶面であるｃ面（結晶軸ａ，ｂ，
ｃにより定義される）が、通電方向に対して平行に配向
するようにｐ形熱電半導体１及びｎ形熱電半導体２を導
電性接合部材３と一体化した点に特徴がある。なお、一
体化した後の工程は実施形態１と同様なので説明を省略
する。In the present embodiment, since the conductive bonding members 3 constituting the small block body 5 can be processed collectively over a wide range, the time for the step of forming the electrodes 6 can be reduced. , And productivity is improved. (Embodiment 11) In this embodiment, the c-plane (crystal axes a, b,
c) is characterized in that the p-type thermoelectric semiconductor 1 and the n-type thermoelectric semiconductor 2 are integrated with the conductive bonding member 3 so as to be oriented in parallel with the direction of conduction. The steps after the integration are the same as those in the first embodiment, and the description is omitted.

【００６８】ところで、上記実施形態でｐ形熱電半導体
１の主材料である（Ｓｂ，Ｂｉ）2（Ｔｅ，Ｓｅ）3 系
化合物半導体の結晶及びｎ形熱電半導体２の主材料であ
るＢｉ2 （Ｔｅ，Ｓｅ）3 系化合物半導体の結晶は菱面
体構造をもつ層状化合物であり、その結晶対称性から熱
電気輸送現象に大きな異方性を示す（大きな異方性を有
するので、通電方向により導電率に大きな違いが生じ
る）。この単結晶のｃ軸に垂直な方向（つまり、ｃ面に
平行な方向）は、ｃ軸に平行な方向よりも導電率が大き
いので熱電性能指数Ｚが大きく、またａ軸方向が結晶の
成長方向であるため実用には一方向凝固によって成長方
向にａ軸をそろえた大きな結晶粒からなる多結晶材料が
使用されている。なお、ｃ面に平行な方向への結晶構造
がイオン結合と共有結合とで構成されているのに対し、
ｃ面に垂直な方向（ｃ軸方向）へは分子間結合が含まれ
ているので、ｃ軸方向への導電率が減少する。Incidentally, in the above embodiment, the crystal of the (Sb, Bi) 2 (Te, Se) 3 -based compound semiconductor, which is the main material of the p-type thermoelectric semiconductor 1, and Bi 2 (the main material of the n-type thermoelectric semiconductor 2 ). The crystal of the (Te, Se) 3 -based compound semiconductor is a layered compound having a rhombohedral structure and exhibits a large anisotropy in the thermoelectric transport phenomenon due to its crystal symmetry. Big differences in rates). The direction perpendicular to the c-axis of this single crystal (that is, the direction parallel to the c-plane) is higher in conductivity than the direction parallel to the c-axis, so the thermoelectric figure of merit Z is larger, and the a-axis direction is crystal growth. Because of the direction, a polycrystalline material composed of large crystal grains whose a-axis is aligned in the growth direction by unidirectional solidification is practically used. In addition, while the crystal structure in the direction parallel to the c-plane is composed of ionic bonds and covalent bonds,
Since the intermolecular bond is included in the direction perpendicular to the c-plane (c-axis direction), the conductivity in the c-axis direction decreases.

【００６９】本実施形態では、図１１に示すようなｐ熱
電半導体インゴット１７（ｎ形熱電半導体インゴット１
８）をｃ面が熱電変換モジュール１００を構成した場合
の通電方向に対して平行に配向するように角柱状（もし
くは平板状）に切り出し（図１１（ｂ）参照）、該切り
出されたｐ形熱電半導体１及びｎ形熱半導体２を導電性
接合部材３を介在させて図１１（ｃ）に示すブロック体
４を形成する。なお、図１１（ｄ）に示すように、ｐ熱
電半導体インゴット１７（ｎ形熱電半導体インゴット１
８）及びｐ形熱電半導体１（ｎ形熱電半導体２）は結晶
面が一軸方向（熱電変換モジュール１００を構成した場
合における通電方向、つまり、図１１（ｃ）の上下方
向）に配向している。In the present embodiment, the p thermoelectric semiconductor ingot 17 (the n-type thermoelectric semiconductor ingot 1) as shown in FIG.
8) is cut out into a prismatic (or flat) shape so that the c-plane is oriented parallel to the direction of current flow when the thermoelectric conversion module 100 is configured (see FIG. 11B), and the cut out p-type The block body 4 shown in FIG. 11C is formed by interposing the thermoelectric semiconductor 1 and the n-type heat semiconductor 2 with the conductive bonding member 3 interposed therebetween. As shown in FIG. 11D, the p thermoelectric semiconductor ingot 17 (the n-type thermoelectric semiconductor ingot 1)
8) and the p-type thermoelectric semiconductor 1 (n-type thermoelectric semiconductor 2) have their crystal planes oriented in a uniaxial direction (the energizing direction when the thermoelectric conversion module 100 is configured, that is, the vertical direction in FIG. 11C). .

【００７０】しかして、本実施形態では、各熱電半導体
１，２の熱電性能指数Ｚが高く得られる方向と熱電変換
モジュール１００を構成した場合における各熱電半導体
１，２の通電方向とを一致させてあるので、熱電変換モ
ジュール１００の熱電性能を向上させることができる。
なお、（Ｓｂ，Ｂｉ）2 （Ｔｅ，Ｓｅ）3 系化合物半導
体、Ｂｉ2 （Ｔｅ，Ｓｅ）3 系化合物半導体の熱電特性
は、焼結により形成される場合にも単結晶に類似の異方
性を有し、焼結前のプレス方向が単結晶のｃ軸に対応す
るので、焼結により形成される熱電半導体を用いた場合
にも、ｃ面に相当する面に平行な面が上記通電方向に対
して平行となる。In this embodiment, the direction in which the thermoelectric performance index Z of each of the thermoelectric semiconductors 1 and 2 is obtained is made to match the direction in which the thermoelectric semiconductors 1 and 2 are energized when the thermoelectric conversion module 100 is constructed. Therefore, the thermoelectric performance of the thermoelectric conversion module 100 can be improved.
The thermoelectric properties of the (Sb, Bi) 2 (Te, Se) 3 -based compound semiconductor and the Bi 2 (Te, Se) 3 -based compound semiconductor are similar to those of a single crystal even when formed by sintering. Since the pressing direction before sintering corresponds to the c-axis of the single crystal, even when a thermoelectric semiconductor formed by sintering is used, the plane parallel to the plane corresponding to the c-plane is energized. It is parallel to the direction.

【００７１】（実施形態１２）本実施形態では、実施形
態１の製造方法により作製した熱電変換モジュール１０
０を図１２（ａ）に示すように一面開口した直方体状の
充填用容器１１０内にセッティングする。ここに、充填
用容器１１０は、離型しやすいように内周面に適宜の表
面処理を施してある。(Embodiment 12) In this embodiment, the thermoelectric conversion module 10 manufactured by the manufacturing method of Embodiment 1
0 is set in a rectangular parallelepiped filling container 110 which is open on one side as shown in FIG. Here, the filling container 110 is subjected to an appropriate surface treatment on the inner peripheral surface so as to be easily released.

【００７２】次に、図１２（ｂ）に示すように、容器１
１１内に貯蔵されている液状の発泡性ポリスチレンのよ
うな発泡性樹脂よりなる絶縁性材料１１２を、導電性接
合部材３の一部を除去することにより形成された除去部
（ｐ形熱電半導体１とｎ形熱電半導体２と電極６とで囲
まれる空間）に充填し、所定の硬化条件（例えば１２０
℃で２時間のベーキング）で絶縁性材料１１２を硬化さ
せる。絶縁性材料１１２が硬化した後、離型して熱電変
換モジュール１００の上下を逆にして、同様の処理を行
うことにより、図１２（ｃ）に示すような熱電変換モジ
ュール１００’が得られる。Next, as shown in FIG.
A removing portion (p-type thermoelectric semiconductor 1) formed by removing a part of the conductive joining member 3 is made of an insulating material 112 made of a foaming resin such as a liquid foaming polystyrene stored in the inside. And a space surrounded by the n-type thermoelectric semiconductor 2 and the electrode 6), and cured under predetermined curing conditions (for example, 120
(Baking at 2 ° C. for 2 hours) to cure the insulating material 112. After the insulating material 112 is cured, the mold is released, the thermoelectric conversion module 100 is turned upside down, and the same processing is performed to obtain a thermoelectric conversion module 100 ′ as shown in FIG. 12C.

【００７３】なお、熱電変換モジュール１００’の上面
及び下面に露出すべき電極６の表面に絶縁性材料１１２
が付着したり、あるいは、絶縁性材料１１２の過不足そ
の他により、熱電変換モジュール１００’の放熱面（例
えば上記上面）や吸着面（上記下面）の平坦度が損なわ
れたときは、薬液で清浄したりあるいは機械的研磨によ
り所望の平坦度が得られるように加工すればよい。The surface of the electrode 6 to be exposed on the upper and lower surfaces of the thermoelectric conversion module 100 ′ is coated with an insulating material 112.
When the flatness of the heat radiating surface (for example, the upper surface) or the adsorption surface (the lower surface) of the thermoelectric conversion module 100 ′ is impaired due to the adhesion of the insulating material 112, the excess or deficiency of the insulating material 112, etc. Or mechanical polishing to obtain a desired flatness.

【００７４】本実施形態における熱電変換モジュール１
００’では、熱電変換モジュール１００の上記除去部に
絶縁性材料１１２が充填されているので、各熱電半導体
１，２の機械的強度及び電極６の接合強度が向上して耐
衝撃性、耐振動性を高めることができるとともに、防湿
性、酸化防止性、電気絶縁性などを高めることができ、
さらに、ホイスカー（ウイスカー）の発生を抑制するこ
ともできる。また、上記絶縁性材料１１２（及び後述の
絶縁性材料１１３、１１４、１１５）は比較的熱伝導率
が低い（０．０１Ｗ／ｍＫ〜０．５Ｗ／ｍＫ程度）の
で、吸着面と放熱面との間の熱短絡を抑制することがで
きる。The thermoelectric conversion module 1 according to the present embodiment
In 00 ′, since the insulating material 112 is filled in the removed portion of the thermoelectric conversion module 100, the mechanical strength of each of the thermoelectric semiconductors 1 and 2 and the bonding strength of the electrode 6 are improved, and the shock resistance and vibration resistance are improved. Can increase the moisture resistance, antioxidant properties, electrical insulation, etc.,
Further, generation of whiskers (whiskers) can be suppressed. Further, the insulating material 112 (and insulating materials 113, 114, and 115 described later) has a relatively low thermal conductivity (about 0.01 W / mK to 0.5 W / mK), so that the adsorbing surface and the heat dissipating surface are hardly separated. Can be suppressed.

【００７５】（実施形態１３）ところで、実施形態１２
では導電性接合部材３の一部が除去されることにより形
成された除去部に発泡性樹脂よりなる絶縁性材料１１２
を充填していたが、本実施形態では、上記除去部に、図
１３に示すように、熱加硫型シリコーンゴム（シリコー
ン樹脂）のような比較的柔軟性の高い樹脂よりなる絶縁
性材料１１３を充填し、所定の硬化条件（例えば１００
℃で６時間のベーキング）で絶縁性材料１１３を硬化さ
せる。(Embodiment 13) Embodiment 12
Then, the insulating material 112 made of a foaming resin is provided on a removed portion formed by removing a part of the conductive joining member 3.
However, in the present embodiment, as shown in FIG. 13, the insulating material 113 made of a relatively flexible resin such as a heat-curable silicone rubber (silicone resin) is provided in the above-described removing portion. And curing under predetermined curing conditions (for example, 100
The insulating material 113 is cured by baking at 6 ° C. for 6 hours.

【００７６】なお、熱電変換モジュール１００’の上面
及び下面に露出すべき電極６の表面に絶縁性材料１１３
が付着したり、あるいは、絶縁性材料１１３の過不足そ
の他により、熱電変換モジュール１００’の放熱面（例
えば上記上面）や吸着面（上記下面）の平坦度が損なわ
れたときは、薬液で清浄したりあるいは機械的研磨によ
り所望の平坦度が得られるように加工すればよい。The surface of the electrode 6 to be exposed on the upper and lower surfaces of the thermoelectric conversion module 100 ′ has an insulating material 113.
When the flatness of the heat radiation surface (for example, the upper surface) or the adsorption surface (the lower surface) of the thermoelectric conversion module 100 ′ is impaired due to adhesion of the insulating material 113, excess or deficiency of the insulating material 113, etc. Or mechanical polishing to obtain a desired flatness.

【００７７】本実施形態における熱電変換モジュール１
００’では、実施形態１の製造方法により作製された熱
電変換モジュール１００の上記除去部に、柔軟性を有す
る絶縁性材料１１３が充填されているので、熱電変換モ
ジュール１００’への通電時に発生する熱応力を緩和す
ることができるとともに、耐衝撃性も向上し、熱電変換
モジュール１００’の信頼性が向上する。The thermoelectric conversion module 1 according to the present embodiment
In the case of 00 ′, since the above-described removed portion of the thermoelectric conversion module 100 manufactured by the manufacturing method of Embodiment 1 is filled with the insulating material 113 having flexibility, it is generated when the thermoelectric conversion module 100 ′ is energized. The thermal stress can be reduced, the impact resistance is improved, and the reliability of the thermoelectric conversion module 100 'is improved.

【００７８】（実施形態１４）ところで、実施形態１２
では導電性接合部材３の一部が除去されることにより形
成された除去部に発泡性樹脂よりなる絶縁性材料１１２
を充填していたが、本実施形態では、上記除去部に、図
１４に示すように、エポキシ系接着剤のような熱電半導
体１，２との接着力が比較的強い（熱電半導体１，２の
引っ張り強度以上の）樹脂よりなる絶縁性材料１１４を
充填し、所定の硬化条件（例えば６０℃で１時間のベー
キング）で絶縁性材料１１４を硬化させる。(Embodiment 14) Embodiment 12
Then, the insulating material 112 made of a foaming resin is provided on a removed portion formed by removing a part of the conductive joining member 3.
However, in the present embodiment, as shown in FIG. 14, the adhesive strength between the removal portion and the thermoelectric semiconductors 1 and 2 such as an epoxy-based adhesive is relatively strong (the thermoelectric semiconductors 1 and 2). Is filled with an insulating material 114 made of a resin (having a tensile strength equal to or higher than the above tensile strength), and the insulating material 114 is cured under predetermined curing conditions (for example, baking at 60 ° C. for 1 hour).

【００７９】なお、熱電変換モジュール１００’の上面
及び下面に露出すべき電極６の表面に絶縁性材料１１４
が付着したり、あるいは、絶縁性材料１１４の過不足そ
の他により、熱電変換モジュール１００’の放熱面（例
えば上記上面）や吸着面（上記下面）の平坦度が損なわ
れたときは、薬液で清浄したりあるいは機械的研磨によ
り所望の平坦度が得られるように加工すればよい。The surface of the electrode 6 to be exposed on the upper and lower surfaces of the thermoelectric conversion module 100 ′ is coated with an insulating material 114.
When the flatness of the heat radiation surface (for example, the upper surface) or the adsorption surface (the lower surface) of the thermoelectric conversion module 100 ′ is impaired due to the adhesion of the insulating material 114, excess or deficiency of the insulating material 114, etc. Or mechanical polishing to obtain a desired flatness.

【００８０】本実施形態では、上記除去部に各熱電半導
体１，２との接着力が比較的大きな絶縁性材料１１４が
充填されているので、絶縁性材料１１４と各熱電半導体
１，２との接合強度が向上し、絶縁性材料１１４の剥離
や脱落を防止することができる。 （実施形態１５）ところで、実施形態１２では導電性接
合部材３の一部が除去されることにより形成された除去
部に発泡性樹脂よりなる絶縁性材料１１２を充填してい
たが、本実施形態では、上記除去部に、図１５に示すよ
うに、例えば高耐熱エポキシ樹脂やポリイミド樹脂のよ
うな高耐熱性（３００℃以上の耐熱性）を有する絶縁性
材料１１５を充填し、所定の硬化条件（例えば１５０℃
で１時間のベーキング）で絶縁性材料１１５を硬化させ
る。In this embodiment, since the above-mentioned removed portion is filled with the insulating material 114 having a relatively large adhesive force with the thermoelectric semiconductors 1 and 2, the insulating material 114 and the thermoelectric semiconductors 1 and 2 are filled with each other. The bonding strength is improved, and peeling or falling off of the insulating material 114 can be prevented. (Embodiment 15) By the way, in Embodiment 12, the removed portion formed by removing a part of the conductive bonding member 3 is filled with the insulating material 112 made of a foaming resin. Then, as shown in FIG. 15, the above-mentioned removed portion is filled with an insulating material 115 having high heat resistance (heat resistance of 300 ° C. or more) such as a high heat-resistant epoxy resin or a polyimide resin, and cured under a predetermined curing condition. (For example, 150 ° C
Baking for one hour) to cure the insulating material 115.

【００８１】なお、熱電変換モジュール１００’の上面
及び下面に露出すべき電極６の表面に絶縁性材料１１５
が付着したり、あるいは、絶縁性材料１１５の過不足そ
の他により、熱電変換モジュール１００’の放熱面（例
えば上記上面）や吸着面（上記下面）の平坦度が損なわ
れたときは、薬液で清浄したりあるいは機械的研磨によ
り所望の平坦度が得られるように加工すればよい。The surface of the electrode 6 to be exposed on the upper and lower surfaces of the thermoelectric conversion module 100 ′ is coated with an insulating material 115.
When the flatness of the heat radiating surface (for example, the upper surface) or the adsorption surface (the lower surface) of the thermoelectric conversion module 100 ′ is impaired due to the adhesion of the insulating material 115 or the excess or deficiency of the insulating material 115, cleaning with a chemical solution is performed. Or mechanical polishing to obtain a desired flatness.

【００８２】本実施形態では、上記除去部に、高耐熱性
（３００℃以上の耐熱性）を有する絶縁性材料１１５が
充填されているので、上記絶縁性材料１１２〜１１４を
充填している場合に比べて絶縁性材料の耐熱性が向上
し、熱電変換モジュール１００’の信頼性が向上する。
また、熱電変換モジュール１００’が焼損するような場
合にあっても絶縁性材料１１５が発火しにくいので、安
全性が向上する。In the present embodiment, the above-mentioned removed portion is filled with the insulating material 115 having high heat resistance (heat resistance of 300 ° C. or more). The heat resistance of the insulating material is improved as compared with the above, and the reliability of the thermoelectric conversion module 100 ′ is improved.
In addition, even when the thermoelectric conversion module 100 ′ is burned, the insulating material 115 does not easily ignite, so that safety is improved.

【００８３】（実施形態１６）本実施形態では、実施形
態１２乃至実施形態１５において絶縁性材料１１２〜１
１５を上記除去部に充填する前に、以下の処理を行う点
に特徴がある。図１６（ａ）に示すような熱電変換モジ
ュール１００を図１６（ｂ）に示すように純水槽１２０
にて純水洗浄した後、図１６（ｃ）に示すように硝酸
（１０％）が充填されたエッチング槽１００に所定時間
だけ浸して熱電変換モジュール１００の表面を粗面化
し、図１６（ｄ）に示すように純水槽１２２にて純水洗
浄し、乾燥させる（図１６（ｅ）参照）。(Embodiment 16) In this embodiment, the insulating materials 112 to 1 in Embodiments 12 to 15 will be described.
It is characterized in that the following processing is performed before filling the above-mentioned removal section with 15. As shown in FIG. 16B, a thermoelectric conversion module 100 as shown in FIG.
Then, as shown in FIG. 16C, the surface of the thermoelectric conversion module 100 is roughened by immersing it in an etching bath 100 filled with nitric acid (10%) for a predetermined time, as shown in FIG. As shown in FIG. 16), the substrate is washed with pure water in a pure water tank 122 and dried (see FIG. 16E).

【００８４】しかして、本実施形態では、熱電変換モジ
ュール１００の表面が化学エッチングにより粗面化され
るので、熱電変換モジュール１００の上記除去部の内周
面における所謂アンカー効果が大きくなり、熱電変換モ
ジュール１００への絶縁性材料１１２〜１１５の接合強
度が向上する。なお、熱電変換モジュール１００の表面
の粗面化の方法は化学エッチングに限定するものではな
く、例えばサンドブラストなどにより行ってもよい。In the present embodiment, however, since the surface of the thermoelectric conversion module 100 is roughened by chemical etching, the so-called anchor effect on the inner peripheral surface of the removed portion of the thermoelectric conversion module 100 increases, and the thermoelectric conversion module 100 The joining strength of the insulating materials 112 to 115 to the module 100 is improved. The method of roughening the surface of the thermoelectric conversion module 100 is not limited to chemical etching, and may be performed by, for example, sandblasting.

【００８５】（実施形態１７）本実施形態では、実施形
態１の製造方法で作製された熱電変換モジュール１００
の上下両面をサンドペーパにより研磨し、さらにプラズ
マエッチングを行うことにより表面の粗面化を行った
後、金属製マスクを装着して、熱電変換モジュール１０
０の放熱面及び吸熱面に、ＤＣプラズマにより所定の条
件（例えば、ＤＣパワー：３０００Ｗ、圧力：４Ｐａ、
ガス：Ａｒ、成膜時間：９０秒）で熱伝導率の高い金属
薄膜１３１（例えば、膜厚が１．０μｍのＭｏ膜）を形
成し、上記金属製マスクを離脱することにより図１７
（ａ）に示す熱電変換モジュール１００”が得られる。
同様に、実施形態１２乃至実施形態１６に示すように上
記除去部に絶縁性材料１１２〜１１５が充填されている
場合であっも、同様の金属製マスクを利用して用いて上
記金属薄膜１３１を形成することにより図１７（ｂ）に
示す熱電変換モジュール１００”が得られる。(Embodiment 17) In the present embodiment, a thermoelectric conversion module 100 manufactured by the manufacturing method of Embodiment 1 is used.
The upper and lower surfaces are polished with sandpaper, and the surface is roughened by plasma etching. Then, a metal mask is attached and the thermoelectric conversion module 10 is mounted.
0, a predetermined condition (for example, DC power: 3000 W, pressure: 4 Pa,
A metal thin film 131 having a high thermal conductivity (for example, a Mo film having a thickness of 1.0 μm) is formed with gas: Ar, film forming time: 90 seconds, and the metal mask is separated from the metal thin film 131 as shown in FIG.
The thermoelectric conversion module 100 ″ shown in FIG.
Similarly, even when the removed portions are filled with the insulating materials 112 to 115 as shown in Embodiments 12 to 16, the metal thin film 131 is formed using the same metal mask. By forming, the thermoelectric conversion module 100 ″ shown in FIG. 17B is obtained.

【００８６】本実施形態では、熱伝導率の高い金属薄膜
１３１により熱電変換モジュール１００（１００’）の
吸熱面及び放熱面（熱電変換モジュール１００の厚み方
向の両面における電極６及び各熱電半導体１，２の表
面）を被膜してあるので、放熱板もしくは絶縁板との良
好な熱伝導性を得ることができるとともに、電極６の接
合部の熱応力を緩和することができる。また、各熱電半
導体１，２や電極６の表面の酸化を抑制するとともに防
湿性を高めることができる。In this embodiment, the heat absorbing surface and the heat radiating surface of the thermoelectric conversion module 100 (100 ′) (the electrodes 6 and the thermoelectric semiconductors 1 and 2 on both sides in the thickness direction of the thermoelectric conversion module 100) are formed by the metal thin film 131 having a high thermal conductivity. 2), good thermal conductivity with the heat radiating plate or the insulating plate can be obtained, and the thermal stress at the joint of the electrodes 6 can be reduced. In addition, the oxidation of the surface of each of the thermoelectric semiconductors 1 and 2 and the electrode 6 can be suppressed, and the moisture resistance can be improved.

【００８７】（実施形態１８）本実施形態では、実施形
態１の製造方法で作製された熱電変換モジュール１００
の上下両面をサンドペーパにより研磨し、さらにプラズ
マエッチングを行うことにより表面の粗面化を行った
後、金属製マスクを装着して、熱電変換モジュール１０
０の放熱面及び吸熱面に、ＲＦプラズマにより所定の条
件（例えば、ＲＦパワー：２００Ｗ、圧力：０．４Ｐ
ａ、ガス：Ａｒ、成膜時間：２０分）で導電性金属膜１
３２（例えば、膜厚が１．０μｍのＳｎ膜）を形成し、
さらに、ＤＣプラズマにより所定の条件（例えば、ＤＣ
パワー：３０００Ｗ、圧力：４Ｐａ、ガス：Ａｒ、成膜
時間：４５秒）で熱伝導率の高い金属薄膜１３１’（例
えば膜厚が０．５μｍのＭｏ膜）を形成し、金属製マス
クを離脱し、その後、電気Ｃｕメッキにより５０μｍの
厚さのＣｕ膜よりなる導電性厚膜１３３を形成すること
により図１８（ａ）に示す熱電変換モジュール１００”
が得られる。同様に、実施形態１２乃至実施形態１６に
示すように上記除去部に絶縁性材料１１２乃至１１５が
充填されている場合であっも、同様の金属製マスクを利
用して導電性金属膜１３２及び上記金属薄膜１３１’を
形成した後に、金属製マスクを離脱して導電性厚膜１３
３を形成することにより図１８（ｂ）に示す熱電変換モ
ジュール１００”が得られる。(Embodiment 18) In this embodiment, a thermoelectric conversion module 100 manufactured by the manufacturing method of Embodiment 1 will be described.
The upper and lower surfaces are polished with sandpaper, and the surface is roughened by plasma etching. Then, a metal mask is attached and the thermoelectric conversion module 10 is mounted.
0 on the heat radiating surface and the heat absorbing surface by RF plasma under predetermined conditions (for example, RF power: 200 W, pressure: 0.4 P
a, gas: Ar, film formation time: 20 minutes) and a conductive metal film 1
32 (for example, a Sn film having a thickness of 1.0 μm);
Further, a predetermined condition (for example, DC
A metal thin film 131 ′ (for example, a 0.5 μm-thick Mo film) having high thermal conductivity is formed at a power of 3000 W, a pressure of 4 Pa, a gas of Ar, and a film formation time of 45 seconds, and the metal mask is removed. Thereafter, a conductive thick film 133 made of a Cu film having a thickness of 50 μm is formed by electric Cu plating, thereby forming the thermoelectric conversion module 100 ″ shown in FIG.
Is obtained. Similarly, even when the removed portions are filled with the insulating materials 112 to 115 as shown in the twelfth to sixteenth embodiments, the conductive metal film 132 and the After forming the metal thin film 131 ', the metal mask is removed and the conductive thick film 13' is removed.
By forming No. 3, a thermoelectric conversion module 100 ″ shown in FIG. 18B is obtained.

【００８８】しかして、本実施形態では、実施形態７に
比べて電極６の接合強度がさらに向上し、また、導電性
厚膜１３３が補助電極として働き電極６への電流の集中
を抑制することができる。また、実施形態１７と同様
に、熱電半導体１，２や電極６表面の酸化防止及び防湿
性向上を図ることができる。 （実施形態１９）本実施形態では、高い熱伝導性を有す
る低粘性エポキシ系樹脂よりなる絶縁性材料１１６を実
施形態１の製造方法で作製された熱電変換モジュール１
００よりも大きな容器に充填し、該熱電変換モジュール
１００を上記容器内の絶縁性材料１１６にディップする
ことにより、図１９（ａ）に示すように、熱電変換モジ
ュール１００の全面に絶縁性材料１１６がコーティング
される。同様に、実施形態１２乃至実施形態１６に示す
ように上記除去部に絶縁性材料１１２乃至１１５が充填
されている場合であっも、熱電変換モジュール１００’
を上記容器内の絶縁性材料１１６にディップすることに
より、図１９（ｂ）に示すように、熱電変換モジュール
１００’の表面に絶縁性材料１１６がコーティングされ
る。In the present embodiment, however, the bonding strength of the electrode 6 is further improved as compared with the seventh embodiment, and the conductive thick film 133 functions as an auxiliary electrode to suppress current concentration on the electrode 6. Can be. Further, similarly to the seventeenth embodiment, it is possible to prevent the oxidation of the surface of the thermoelectric semiconductors 1 and 2 and the surface of the electrode 6 and to improve the moisture resistance. (Embodiment 19) In this embodiment, a thermoelectric conversion module 1 manufactured by the manufacturing method of Embodiment 1 is manufactured by using an insulating material 116 made of a low-viscosity epoxy resin having high thermal conductivity.
19, the thermoelectric conversion module 100 is dipped into the insulating material 116 in the container, and as shown in FIG. Is coated. Similarly, even in the case where the removed portions are filled with the insulating materials 112 to 115 as shown in the twelfth to sixteenth embodiments, the thermoelectric conversion module 100 ′
Is dipped into the insulating material 116 in the container, so that the surface of the thermoelectric conversion module 100 ′ is coated with the insulating material 116 as shown in FIG.

【００８９】本実施形態では、熱電変換モジュール１０
０もしくは１００’の全面に絶縁性材料１１６がコーテ
ィングされるので、放熱板や吸熱板などの熱交換器との
電気絶縁性を高めることができるとともに、実施形態１
７と同様に、熱電半導体１，２や電極６表面の酸化防止
及び防湿性向上を図ることができる。In this embodiment, the thermoelectric conversion module 10
Since the insulating material 116 is coated on the entire surface of 0 or 100 ', the electrical insulation with a heat exchanger such as a heat radiating plate or a heat absorbing plate can be improved, and the first embodiment can be used.
As in the case of 7, the surface of the thermoelectric semiconductors 1, 2 and the electrode 6 can be prevented from being oxidized and the moisture-proof property can be improved.

【００９０】[0090]

【発明の効果】請求項１の発明は、ｐ形熱電半導体とｎ
形熱電半導体とが電極を介して同一方向に交互に配設さ
れるとともに接合され、かつ上記電極が該配設方向に直
交する厚み方向の両端側に交互に設けられる熱電変換モ
ジュールの製造方法であって、ｐ形熱電半導体とｎ形熱
電半導体との間に導電性接合部材を設けて接合し一体化
することによりブロック体を形成する第１の工程と、上
記ブロック体を各熱電半導体と導電性接合部材との接合
面に対して略直交するように切断することにより所望の
厚さの小ブロック体を形成する第２の工程と、小ブロッ
ク体の厚み方向の一端側と他端側とから交互に導電性接
合部材の一部を除去することにより導電性接合部材より
なる上記電極を形成する第３の工程とを有するので、導
電性接合部材と各熱電半導体とを接合してブロック体を
形成した後にブロック体を所望の厚さに切断し、導電性
接合部材を部分的に除去することにより電極を形成する
から、各熱電半導体を別々に所望の大きさに成形する必
要がなく、所望の大きさに成形された各熱電半導体を配
設する工程や各熱電半導体ごとに電極を接合するための
工程も不要となるから、製造工程の簡略化を図ることが
でき、歩留りを向上できるとともに、熱電変換モジュー
ルの低コスト化を図ることができるという効果がある。
また、導電性接合部材のみを除去することにより電極を
形成できるので、比較的単価の高い熱電半導体を有効に
利用することができるとともに、熱電半導体の割れや破
損が発生しにくく材料歩留りや製品歩留りの向上を図る
ことができるという効果がある。また、第１の工程と第
２の工程とにより熱電変換モジュールのサイズが決まる
ので、熱電変換モジュールの形状の制御が容易であり、
熱電変換モジュールの小型化を図ることができるととも
に、サイズの異なる熱電変換モジュールを容易に作製す
ることができるという効果がある。さらに、熱電変換モ
ジュールの放熱面及び吸熱面となる小ブロック体の厚み
方向に直交する両面を略平滑に形成することができるの
で、放熱面及び吸熱面と熱交換基板もしくは熱交換器と
の接合部の熱損失の減少を図ることができ、高性能で信
頼性の高い熱電変換モジュールを製造することができる
という効果がある。According to the present invention, the p-type thermoelectric semiconductor and the n-type
And a thermoelectric semiconductor are alternately arranged and joined in the same direction via electrodes, and the electrodes are alternately provided on both ends in a thickness direction orthogonal to the arrangement direction. A first step of providing a conductive joining member between the p-type thermoelectric semiconductor and the n-type thermoelectric semiconductor and joining and integrating the thermoelectric semiconductor to form a block body; A second step of forming a small block body having a desired thickness by cutting so as to be substantially orthogonal to a bonding surface with the sex bonding member, and one end and the other end in the thickness direction of the small block body. And a third step of forming the electrode made of the conductive bonding member by alternately removing a part of the conductive bonding member from the above, so that the conductive bonding member and each thermoelectric semiconductor are bonded to each other to form a block body. After forming Since the electrodes are formed by cutting the metal body to a desired thickness and partially removing the conductive bonding member, it is not necessary to separately mold each thermoelectric semiconductor to a desired size, and to obtain a desired size. The process of disposing the thermoelectric semiconductors formed in the same manner and the process of bonding the electrodes for each thermoelectric semiconductor are not required, so that the manufacturing process can be simplified, the yield can be improved, and the thermoelectric conversion can be performed. There is an effect that the cost of the module can be reduced.
In addition, since the electrode can be formed by removing only the conductive bonding member, the thermoelectric semiconductor having a relatively high unit price can be effectively used, and the thermoelectric semiconductor is hardly cracked or damaged, and the material yield and the product yield are reduced. There is an effect that it is possible to achieve improvement. Further, since the size of the thermoelectric conversion module is determined by the first step and the second step, it is easy to control the shape of the thermoelectric conversion module,
The thermoelectric conversion module can be downsized, and thermoelectric conversion modules having different sizes can be easily manufactured. Furthermore, since both surfaces orthogonal to the thickness direction of the small block body serving as the heat-radiating surface and the heat-absorbing surface of the thermoelectric conversion module can be formed substantially smooth, the joint between the heat-radiating surface and the heat-absorbing surface and the heat exchange substrate or the heat exchanger can be made. This has the effect of reducing the heat loss of the part and producing a high-performance and highly reliable thermoelectric conversion module.

【００９１】請求項２の発明は、請求項１の発明におい
て、導電性接合部材として各熱電半導体と同程度の線膨
張率及び変形抵抗を有する金属を用い、導電性接合部材
と各熱電半導体とを押し出し加工により接合するので、
押し出し加工により導電性接合部材と各熱電半導体との
接合が行われるから、一括して導電性接合部材と各熱電
半導体とを接合することができるという効果がある。ま
た、各熱電半導体と導電性接合部材との線膨張率が同程
度であることから、熱電変換モジュールへの通電時に電
極の接合界面における熱応力の発生を抑制することがで
き、信頼性が向上するという効果がある。また、各熱電
半導体と導電性接合部材との変形抵抗が同程度であるか
ら、押し出し加工時の形状制御が容易となるという効果
がある。また、導電性接合部材と各熱電半導体とを押し
出し加工により接合するので、押し出し材を切断するこ
とで一度に大量のブロック体を形成することが可能であ
り、生産性が向上するという効果がある。According to a second aspect of the present invention, in the first aspect of the present invention, a metal having substantially the same linear expansion coefficient and deformation resistance as each thermoelectric semiconductor is used as the conductive bonding member, and the conductive bonding member and each thermoelectric semiconductor are connected to each other. Are joined by extrusion.
Since the bonding between the conductive bonding member and each thermoelectric semiconductor is performed by the extrusion, there is an effect that the conductive bonding member and each thermoelectric semiconductor can be bonded together. In addition, since the coefficient of linear expansion between each thermoelectric semiconductor and the conductive bonding member is substantially the same, it is possible to suppress the occurrence of thermal stress at the bonding interface of the electrodes when power is supplied to the thermoelectric conversion module, thereby improving reliability. There is an effect of doing. Further, since the deformation resistance of each thermoelectric semiconductor and the conductive bonding member is substantially the same, there is an effect that the shape control at the time of extrusion processing is facilitated. In addition, since the conductive bonding member and each thermoelectric semiconductor are bonded by extrusion, it is possible to form a large number of blocks at once by cutting the extruded material, which has the effect of improving productivity. .

【００９２】請求項３の発明は、請求項２の発明におい
て、導電性接合部材を内部に複数の収納室が一方向に列
設されたカプセルとし、ｐ形熱電半導体粉末とｎ形熱電
半導体粉末とをカプセルの所定の収納室に充填した後
に、押し出し加工を行うことにより導電性接合部材と各
熱電半導体とを接合するので、押し出し形状の制御が容
易になるとともに、押し出し加工により押し出された熱
電半導体が多結晶になり、熱電半導体の機械的強度が向
上するという効果がある。また、押し出し加工前の熱電
半導体を粉末としたことにより押し出し加工時における
熱電半導体の変形抵抗が小さくなるので、押し出し速度
が向上し生産性が向上するという効果がある。According to a third aspect of the present invention, in the second aspect of the present invention, the conductive bonding member is a capsule in which a plurality of storage chambers are arranged in one direction, and the p-type thermoelectric semiconductor powder and the n-type thermoelectric semiconductor powder are provided. After filling in the predetermined storage chamber of the capsule, the conductive joining member and each thermoelectric semiconductor are joined by performing the extrusion, so that the control of the extrusion shape is facilitated and the thermoelectric extruded by the extrusion is formed. There is an effect that the semiconductor becomes polycrystalline and the mechanical strength of the thermoelectric semiconductor is improved. Further, since the thermoelectric semiconductor before the extrusion is made into powder, the deformation resistance of the thermoelectric semiconductor during the extrusion is reduced, so that there is an effect that the extrusion speed is improved and the productivity is improved.

【００９３】請求項４の発明は、請求項２の発明におい
て、導電性接合部材を内部に複数の収納室が一方向に列
設されたカプセルとし、ｐ形熱電半導体圧粉体とｎ形熱
電半導体圧粉体とをカプセルの所定の収納室に充填した
後に、押し出し加工を行うことにより導電性接合部材と
各熱電半導体とを接合するので、押し出し加工前の熱電
半導体を圧粉体にしたことにより、粉末の場合に比べて
取扱いが容易になるとともに、熱電半導体の酸化を抑制
することができるという効果がある。According to a fourth aspect of the present invention, in the second aspect of the invention, the conductive bonding member is a capsule in which a plurality of storage chambers are arranged in one direction, and the p-type thermoelectric semiconductor compact and the n-type thermoelectric compact are formed. After the semiconductor green compact is filled in a predetermined storage chamber of the capsule, the conductive joining member and each thermoelectric semiconductor are joined by performing the extrusion, so that the thermoelectric semiconductor before the extrusion is formed into a green compact. Thereby, it is easier to handle as compared with the case of powder, and there is an effect that oxidation of the thermoelectric semiconductor can be suppressed.

【００９４】請求項５の発明は、請求項３又は請求項４
の発明において、押し出し加工後に、押し出された押し
出し部材を焼結するので、押し出し加工後に加熱処理が
行われるから、熱電半導体の強度の向上及び熱電半導体
と導電性接合部材との接合強度の向上が図られるという
効果がある。請求項６の発明は、請求項１の発明におい
て、導電性接合部材として各熱電半導体と同程度の弾性
率を有する金属を用い、各熱電半導体として熱電半導体
粉末を用い、ホットプレスにより各熱電半導体と導電性
接合部材とを接合するので、加圧と焼結とが同時に行わ
れるから、各熱電半導体の機械的強度が向上し、結果と
して熱電変換モジュールの機械的強度が向上するという
効果がある。また、ホットプレスを行うことにより、各
熱電半導体の結晶面が一軸に配向するので、各熱電半導
体の熱電特性が向上するという効果がある。The invention of claim 5 is the invention of claim 3 or claim 4.
In the invention of the above, since the extruded extruded member is sintered after the extruding process, the heat treatment is performed after the extruding process, so that the strength of the thermoelectric semiconductor and the bonding strength between the thermoelectric semiconductor and the conductive joining member are improved. This has the effect of being achieved. According to a sixth aspect of the present invention, in the first aspect, a metal having the same elastic modulus as each thermoelectric semiconductor is used as the conductive bonding member, a thermoelectric semiconductor powder is used as each thermoelectric semiconductor, and each thermoelectric semiconductor is hot-pressed. And the conductive joining member, the pressing and sintering are performed simultaneously, so that the mechanical strength of each thermoelectric semiconductor is improved, and as a result, the mechanical strength of the thermoelectric conversion module is improved. . In addition, by performing hot pressing, the crystal plane of each thermoelectric semiconductor is uniaxially oriented, so that there is an effect that the thermoelectric characteristics of each thermoelectric semiconductor are improved.

【００９５】請求項７の発明は、請求項１の発明におい
て、導電性接合部材として各熱電半導体と同程度の弾性
率を有する金属を用い、各熱電半導体として熱電半導体
粉末を用い、熱間静水圧プレスにより各熱電半導体と導
電性接合部材とを接合するので、加圧焼結によりネック
の再結合が促進され各熱電半導体の機械的強度が向上
し、結果として熱電変換モジュールの機械的強度が向上
するという効果がある。According to a seventh aspect of the present invention, in the first aspect of the invention, a metal having the same elastic modulus as each thermoelectric semiconductor is used as the conductive bonding member, and a thermoelectric semiconductor powder is used as each thermoelectric semiconductor. Since each thermoelectric semiconductor and the conductive joining member are joined by the hydraulic press, the recombination of the neck is promoted by the pressure sintering, and the mechanical strength of each thermoelectric semiconductor is improved. As a result, the mechanical strength of the thermoelectric conversion module is improved. There is an effect of improving.

【００９６】請求項８の発明は、請求項１の発明におい
て、各熱電半導体と導電性接合部材との間に、導電性を
有し且つ各熱電半導体へ拡散可能であって該拡散による
各熱電半導体の性能劣化の少ない導電性中間部材を介在
させてブロック体を形成するので、導電性中間部材の構
成元素が各熱電半導体に拡散することにより、各熱電半
導体の性能劣化なしに、各熱電半導体と導電性接合部材
との接合強度を高めることができるという効果がある。According to an eighth aspect of the present invention, in the first aspect of the present invention, there is provided a conductive material between each thermoelectric semiconductor and the conductive joining member, the thermoelectric semiconductor being capable of being diffused into each thermoelectric semiconductor, and each thermoelectric semiconductor being formed by the diffusion. Since the block body is formed by interposing a conductive intermediate member with little deterioration in the performance of the semiconductor, the constituent elements of the conductive intermediate member diffuse into each thermoelectric semiconductor, so that each thermoelectric semiconductor does not deteriorate without the performance of each thermoelectric semiconductor. There is an effect that the joining strength between the metal and the conductive joining member can be increased.

【００９７】請求項９の発明は、請求項１又は請求項８
の発明において、各熱電半導体と導電性接合部材との間
に、導電性を有し且つ他の部材からの拡散を防止する拡
散防止部材を介在させてブロック体を形成するので、拡
散防止部材によって、この拡散防止部材を通る相互拡散
が抑制されるから、拡散による各熱電半導体と導電性接
合部材との接合強度の低下や熱電半導体の性能の経時劣
化を防止することができるという効果がある。The ninth aspect of the present invention relates to the first or eighth aspect.
In the invention, since a block body is formed between each thermoelectric semiconductor and the conductive bonding member by interposing a diffusion preventing member having conductivity and preventing diffusion from other members, the diffusion preventing member Since the mutual diffusion through the diffusion preventing member is suppressed, it is possible to prevent a reduction in bonding strength between each thermoelectric semiconductor and the conductive bonding member due to the diffusion and a deterioration with time of the performance of the thermoelectric semiconductor.

【００９８】請求項１０の発明は、請求項２の発明にお
いて、各熱電半導体と導電性接合部材との間に、高い延
性を有する導電性中間部材を介在させて押し出し加工を
行うので、加圧接合時に接合界面に発生する応力を低減
できるから、押し出し形状の制御が容易になるととも
に、押し出し加工により形成されたブロック体を切断す
る工程における歩留りが向上するという効果がある。According to a tenth aspect of the present invention, in the invention of the second aspect, since the extruding process is performed by interposing a conductive intermediate member having high ductility between each of the thermoelectric semiconductors and the conductive joining member, pressure is applied. Since the stress generated at the bonding interface at the time of bonding can be reduced, the extrusion shape can be easily controlled, and the yield in the step of cutting the block body formed by the extrusion processing can be improved.

【００９９】請求項１１の発明は、請求項１の発明にお
いて、導電性接合部材及び熱電半導体の少なくとも一方
の表面を、機械的切削、化学エッチング、サンドブラス
トなどにより粗面化した後に、各熱電半導体と導電性接
合部材とを接合するので、接合面の面積が増大し、接合
強度が向上するという効果がある。請求項１２の発明
は、請求項８又は請求項１０の発明において、導電性中
間部材を容器状にし、該容器状に形成された導電性中間
層材に熱電半導体を充填した後にブロック体を形成する
ので、導電性中間部材の厚さを均一にすることができる
とともに、製造工程の省力化を図ることができるという
効果がある。An eleventh aspect of the present invention is the invention according to the first aspect, wherein at least one surface of the conductive bonding member and the thermoelectric semiconductor is roughened by mechanical cutting, chemical etching, sand blasting or the like, and then each thermoelectric semiconductor is formed. And the conductive joining member, the effect of increasing the area of the joining surface and improving the joining strength is obtained. According to a twelfth aspect of the present invention, in the invention of the eighth or tenth aspect, the conductive intermediate member is formed into a container, and the conductive intermediate material formed in the container is filled with a thermoelectric semiconductor to form a block body. Therefore, there is an effect that the thickness of the conductive intermediate member can be made uniform and labor saving of the manufacturing process can be achieved.

【０１００】請求項１３の発明は、請求項８又は請求項
１０又は請求項１１の発明において、ブロック体を形成
する前に、導電性接合部材の表面に、メッキ、スパッタ
リング、ペースト塗布等のいずれかの方法により導電性
中間部材を形成する工程を有するので、導電性接合部材
と導電性中間層部材との接合強度が向上するという効果
がある。According to a thirteenth aspect of the present invention, in any one of the eighth, tenth, and eleventh aspects of the present invention, before forming the block, any one of plating, sputtering, paste application, and the like may be applied to the surface of the conductive bonding member. Since the method includes the step of forming the conductive intermediate member by the above method, there is an effect that the bonding strength between the conductive bonding member and the conductive intermediate layer member is improved.

【０１０１】請求項１４の発明は、請求項８又は請求項
１０又は請求項１１の発明において、ブロック体を形成
する前に、各熱電半導体の表面に、メッキ、スパッタリ
ング、ペースト塗布等のいずれかの方法により導電性中
間部材を形成する工程を有するので、導電性接合部材と
導電性中間層部材との接合強度が向上するという効果が
ある。According to a fourteenth aspect of the present invention, in any one of the eighth, tenth, and eleventh aspects, any one of plating, sputtering, paste application, and the like is applied to the surface of each thermoelectric semiconductor before the block body is formed. Since the method includes the step of forming the conductive intermediate member by the method described above, there is an effect that the bonding strength between the conductive bonding member and the conductive intermediate layer member is improved.

【０１０２】請求項１５の発明は、請求項１の発明にお
いて、上記第３の工程は、導電性接合部材の一部をダイ
シングソーなどを用いた機械加工により除去するので、
加工時間を短くできるとともに熱負荷が小さく、生産性
が向上するという効果がある。請求項１６の発明は、請
求項１の発明において、上記第３の工程は、導電性接合
部材の一部をレーザにより除去するので、請求項１５の
発明に比べて微細加工が可能となり、熱電変換モジュー
ルの小型化が可能となるという効果がある。According to a fifteenth aspect of the present invention, in the first aspect of the invention, in the third step, a part of the conductive bonding member is removed by machining using a dicing saw or the like.
There is an effect that the processing time can be shortened, the heat load is small, and the productivity is improved. According to a sixteenth aspect of the present invention, in the first aspect of the present invention, in the third step, a part of the conductive bonding member is removed by a laser. There is an effect that the conversion module can be downsized.

【０１０３】請求項１７の発明は、請求項１の発明にお
いて、上記第３の工程は、小ブロック体を導電性接合部
材の除去部が開孔されたマスクを設けた後に、サンドブ
ラストにより導電性接合部材の一部を除去するので、マ
スクを併用することにより広範囲での加工が可能とな
り、生産性が向上するという効果がある。請求項１８の
発明は、請求項１の発明において、熱電変換モジュール
への通電時に各熱電半導体の結晶面が通電方向に対して
平行に配向するように各熱電半導体を形成するので、熱
電半導体の性能が高くなる方向と熱電半導体への通電方
向とが一致するから、熱電変換モジュールの性能が向上
するという効果がある。According to a seventeenth aspect of the present invention, in the first aspect of the present invention, in the third step, after the small block body is provided with a mask in which the removed portion of the conductive joining member is opened, the small block body is subjected to conductive blasting by sandblasting. Since a part of the joining member is removed, a wide range of processing can be performed by using a mask in combination, which has an effect of improving productivity. The invention of claim 18 is the invention of claim 1, wherein each thermoelectric semiconductor is formed such that the crystal plane of each thermoelectric semiconductor is oriented in parallel to the direction of current when the thermoelectric conversion module is energized. Since the direction in which the performance increases and the direction in which the thermoelectric semiconductor is energized coincide with each other, there is an effect that the performance of the thermoelectric conversion module is improved.

【０１０４】請求項１９の発明は、請求項１の発明にお
いて、導電性接合部材が除去された除去部を樹脂などの
絶縁性材料で充填するので、熱電半導体の強度及び電極
の接合強度が向上し、耐衝撃性、耐振動性が向上し、防
湿、酸化防止、電気絶縁、ホイスカー発生抑制などを図
ることができるという効果がある。請求項２０の発明
は、請求項１９の発明において、絶縁性材料として熱伝
導率が略０．０１Ｗ／ｍＫ乃至略０．５Ｗ／ｍＫの低熱
伝導率材料を使用するので、熱電変換モジュールの吸熱
面と放熱面との間の熱短絡が抑制され、熱電変換モジュ
ールの性能が向上するという効果がある。According to a nineteenth aspect, in the first aspect, the removed portion from which the conductive bonding member has been removed is filled with an insulating material such as a resin, so that the strength of the thermoelectric semiconductor and the bonding strength of the electrode are improved. In addition, shock resistance and vibration resistance are improved, and there is an effect that moisture prevention, oxidation prevention, electric insulation, whisker generation suppression, and the like can be achieved. According to a twentieth aspect, in the nineteenth aspect, a low thermal conductivity material having a thermal conductivity of about 0.01 W / mK to about 0.5 W / mK is used as the insulating material. There is an effect that a thermal short circuit between the surface and the heat radiation surface is suppressed, and the performance of the thermoelectric conversion module is improved.

【０１０５】請求項２１の発明は、請求項１９の発明に
おいて、絶縁性材料としてシリコーン樹脂のような柔軟
性のある材料を使用するので、熱電変換モジュールへの
通電時に発生する熱応力が緩和されるとともに、耐衝撃
性が向上するから、熱電変換モジュールの信頼性が向上
するという効果がある。請求項２２の発明は、請求項１
９の発明において、絶縁性材料としてエポキシ樹脂のよ
うな熱電半導体との接合強度が熱電半導体の引っ張り強
度以上の高接着性樹脂を使用するので、絶縁性材料と熱
電半導体との接合強度が向上し、絶縁性材料の剥離や脱
落を防止することができるという効果がある。請求項２
３の発明は、請求項１９の発明において、絶縁性材料と
して３００℃以上の耐熱性を有するエポキシ樹脂やポリ
イミド樹脂のような高耐熱性材料を使用するので、絶縁
性材料の耐熱性が向上して信頼性が向上するという効果
がある。また、熱電変換モジュールが焼損する場合も容
易に発火しないので、安全性が向上するという効果があ
る。According to a twenty-first aspect of the present invention, since a flexible material such as a silicone resin is used as the insulating material in the nineteenth aspect, the thermal stress generated when the thermoelectric conversion module is energized is reduced. In addition, since the shock resistance is improved, there is an effect that the reliability of the thermoelectric conversion module is improved. The invention of claim 22 is claim 1
In the invention of the ninth aspect, since the bonding strength between the thermoelectric semiconductor and the thermoelectric semiconductor such as epoxy resin is used as the insulating material, the bonding strength between the insulating material and the thermoelectric semiconductor is improved. In addition, there is an effect that peeling or falling off of the insulating material can be prevented. Claim 2
In the invention of claim 3, in the invention of claim 19, since a high heat-resistant material such as an epoxy resin or a polyimide resin having a heat resistance of 300 ° C. or more is used as the insulating material, the heat resistance of the insulating material is improved. This has the effect of improving reliability. In addition, even if the thermoelectric conversion module is burned, it is not easily ignited, so that there is an effect that safety is improved.

【０１０６】請求項２４の発明は、請求項１９乃至請求
項２３の発明において、上記除去部を絶縁性材料で充填
する前に、化学的エッチング、サンドブラスト等により
各熱電半導体の表面を粗面化するので、接合部でのアン
カー効果が大きくなり、絶縁性材料の接合強度が向上す
るという効果がある。請求項２５の発明は、請求項１又
は請求項１９の発明において、上記第１、第２、第３の
工程により形成された熱電変換モジュールの厚み方向の
両面における電極及び各熱電半導体の表面に熱伝導率の
高い金属薄膜を形成する工程を有するので、熱電変換モ
ジュールの厚み方向の両面における電極及び各熱電半導
体の表面に熱伝導率の高い金属薄膜を形成することによ
り、放熱板もしくは絶縁板との良好な熱伝導性を得るこ
とができるとともに、電極の接合部の熱応力を緩和する
ことができるという効果がある。また、熱電半導体や電
極の表面の酸化を抑制するとともに防湿性を高めること
ができるという効果がある。According to a twenty-fourth aspect of the present invention, in any one of the nineteenth to twenty-third aspects, the surface of each thermoelectric semiconductor is roughened by chemical etching, sand blasting or the like before filling the removed portion with an insulating material. Therefore, there is an effect that the anchor effect at the joint is increased and the joining strength of the insulating material is improved. According to a twenty-fifth aspect of the present invention, in the first or nineteenth aspect, the surface of the thermoelectric conversion module formed by the first, second, and third steps on both surfaces in the thickness direction of the thermoelectric conversion module and the surface of each thermoelectric semiconductor is provided. Since the method has a step of forming a metal thin film having a high thermal conductivity, a heat radiating plate or an insulating plate is formed by forming a metal thin film having a high thermal conductivity on the electrodes and the surfaces of each thermoelectric semiconductor on both surfaces in the thickness direction of the thermoelectric conversion module. In addition, it is possible to obtain good thermal conductivity, and to reduce the thermal stress at the junction of the electrodes. In addition, there is an effect that oxidation of the surface of the thermoelectric semiconductor or the electrode can be suppressed and moisture proofness can be improved.

【０１０７】請求項２６の発明は、請求項１又は請求項
１９の発明において、上記第１、第２、第３の工程によ
り形成された熱電変換モジュールの厚み方向の両面にお
ける電極及び各熱電半導体の表面に導電性薄膜を形成も
しくは導電性薄板を接合する工程を有するので、熱電変
換モジュールの厚み方向の両面における電極及び各熱電
半導体の表面に導電性薄膜又は導電性薄板を設けること
により、電極の接合強度を高めることができ、さらに、
電極への電流の集中を抑制することができるという効果
がある。また、熱電半導体や電極の表面の酸化を抑制す
るとともに防湿性を高めることができるという効果があ
る。According to a twenty-sixth aspect of the present invention, in the first or the nineteenth aspect, the electrodes and the thermoelectric semiconductors on both surfaces in the thickness direction of the thermoelectric conversion module formed by the first, second, and third steps are provided. Since a step of forming a conductive thin film on the surface of the thermoelectric conversion module or bonding the conductive thin plate is provided, by providing the conductive thin film or the conductive thin plate on the surface of each of the electrodes and each thermoelectric semiconductor on both surfaces in the thickness direction of the thermoelectric conversion module, Can increase the bonding strength of
There is an effect that current concentration on the electrode can be suppressed. In addition, there is an effect that oxidation of the surface of the thermoelectric semiconductor or the electrode can be suppressed and moisture proofness can be improved.

【０１０８】請求項２７の発明は、請求項１又は請求項
１９又は請求項２５又は請求項２６の発明において、上
記第１、第２、第３の工程により形成された熱電変換モ
ジュールの全面に樹脂等の絶縁性材料をコーティングす
る工程を有するので、熱電変換モジュールの全面に絶縁
性材料をコーティングすることにより、放熱板や吸熱板
など熱交換器との電気絶縁性を高めることができるとと
もに、熱電半導体や電極の表面の酸化を抑制でき、さら
に、防湿性を高めることができるという効果がある。[0108] The invention of claim 27 is the invention according to claim 1 or claim 19 or claim 25 or claim 26, wherein the entire surface of the thermoelectric conversion module formed by the first, second and third steps is provided. Since it has a process of coating an insulating material such as a resin, by coating the entire surface of the thermoelectric conversion module with an insulating material, it is possible to enhance electrical insulation with a heat exchanger such as a heat sink or a heat absorbing plate, There is an effect that oxidation of the surface of the thermoelectric semiconductor or the electrode can be suppressed, and furthermore, the moisture resistance can be improved.

【図面の簡単な説明】[Brief description of the drawings]

【図１】実施形態１の製造方法の説明図である。FIG. 1 is an explanatory diagram of a manufacturing method according to a first embodiment.

【図２】実施形態２の製造方法の説明図である。FIG. 2 is an explanatory diagram of a manufacturing method according to a second embodiment.

【図３】実施形態３の製造方法の説明図である。FIG. 3 is an explanatory diagram of a manufacturing method according to a third embodiment.

【図４】実施形態４の製造方法の説明図である。FIG. 4 is an explanatory diagram of a manufacturing method according to a fourth embodiment.

【図５】実施形態５の製造方法の説明図である。FIG. 5 is an explanatory diagram of a manufacturing method according to a fifth embodiment.

【図６】実施形態６の製造方法の説明図である。FIG. 6 is an explanatory diagram of a manufacturing method according to a sixth embodiment.

【図７】実施形態７の製造方法の説明図である。FIG. 7 is an explanatory diagram of a manufacturing method according to a seventh embodiment.

【図８】実施形態８の製造方法の説明図である。FIG. 8 is an explanatory diagram of a manufacturing method according to an eighth embodiment.

【図９】実施形態９の製造方法の説明図である。FIG. 9 is an explanatory diagram of a manufacturing method according to a ninth embodiment.

【図１０】実施形態１０の製造方法の説明図である。FIG. 10 is an explanatory diagram of the manufacturing method according to the tenth embodiment.

【図１１】実施形態１１の製造方法の説明図である。FIG. 11 is an explanatory diagram of the manufacturing method of the eleventh embodiment.

【図１２】実施形態１２の製造方法の説明図である。FIG. 12 is an explanatory diagram of the manufacturing method of the twelfth embodiment.

【図１３】実施形態１３の製造方法の説明図である。FIG. 13 is an explanatory diagram of the manufacturing method according to the thirteenth embodiment.

【図１４】実施形態１４の製造方法の説明図である。FIG. 14 is an explanatory diagram of the manufacturing method according to the fourteenth embodiment.

【図１５】実施形態１５の製造方法の説明図である。FIG. 15 is an explanatory diagram of the manufacturing method according to the fifteenth embodiment.

【図１６】実施形態１６の製造方法の説明図である。FIG. 16 is an explanatory diagram of the manufacturing method of the sixteenth embodiment.

【図１７】実施形態１７の製造方法の説明図である。FIG. 17 is an explanatory diagram of the manufacturing method of the seventeenth embodiment.

【図１８】実施形態１８の製造方法の説明図である。FIG. 18 is an explanatory diagram of the manufacturing method of the eighteenth embodiment.

【図１９】実施形態１９の製造方法の説明図である。FIG. 19 is an explanatory diagram of the manufacturing method of the nineteenth embodiment.

【符号の説明】[Explanation of symbols]

１ ｐ形熱電半導体 ２ ｎ形熱電半導体 ３ 導電性接合部材 ４ ブロック体 ５ 小ブロック体 ６ 電極 ７ ダイシングソー REFERENCE SIGNS LIST 1 p-type thermoelectric semiconductor 2 n-type thermoelectric semiconductor 3 conductive bonding member 4 block 5 small block 6 electrode 7 dicing saw

【手続補正書】[Procedure amendment]

【提出日】平成９年１０月６日[Submission date] October 6, 1997

【手続補正１】[Procedure amendment 1]

【補正対象書類名】明細書[Document name to be amended] Statement

【補正対象項目名】０００３[Correction target item name] 0003

【補正方法】変更[Correction method] Change

【補正内容】[Correction contents]

【０００３】[0003]

【発明が解決しようとする課題】ところで、熱電変換モ
ジュールの製造にあたっては、モジュールの形状に応じ
て熱電半導体をチップ状もしくは板状などの形状に加工
する必要があるが、Ｂｉ−Ｔｅ−Ｓｂ−Ｓｅ系熱電半導
体は一般的に脆性材料なので、熱電半導体インゴットを
切断する切断工程において材料の割れや欠けが発生した
り、寸法精度を整えるための工程が必要であり、材料歩
留りが低いという問題があった。また、これらの問題の
ため、素子形状（素子の幅や、素子の径など）の小型化
が難しく、高集積化やモジュールの小型化が難しいとい
う問題があり、高電圧低電流型の熱電変換モジュールの
製作が極めて難しいという問題があった。In manufacturing a thermoelectric conversion module, it is necessary to process a thermoelectric semiconductor into a chip shape or a plate shape according to the shape of the module. Since Se-based thermoelectric semiconductors are generally brittle materials , there is a problem in that a material cracking or chipping occurs in a cutting process for cutting the thermoelectric semiconductor ingot, and a process for adjusting dimensional accuracy is required, and the material yield is low. there were. In addition, due to these problems, it is difficult to miniaturize the element shape (element width, element diameter, and the like), and it is difficult to achieve high integration and module miniaturization. There was a problem that module fabrication was extremely difficult.

【手続補正２】[Procedure amendment 2]

【補正対象書類名】明細書[Document name to be amended] Statement

【補正対象項目名】００２５[Correction target item name] 0025

【補正方法】変更[Correction method] Change

【補正内容】[Correction contents]

【００２５】[0025]

【発明の実施の形態】 （実施形態１）本実施形態の熱電変換モジュールの製造
方法を図１に基づいて説明する。なお、熱電半導体の材
料としては、ｐ形熱電半導体１は（Ｓｂ，Ｂｉ） 2 Ｔｅ
3 を主成分とし、ｎ形熱電半導体２はＢｉ2 （Ｔｅ，Ｓ
ｅ）3 を主成分としている。(Embodiment 1) A method for manufacturing a thermoelectric conversion module according to this embodiment will be described with reference to FIG. As a material of the thermoelectric semiconductor, the p-type thermoelectric semiconductor 1 is (Sb, Bi) 2 Te.
3 as a main component, and the n-type thermoelectric semiconductor 2 is made of Bi 2 (Te, S
e) 3 as a main component.

【手続補正３】[Procedure amendment 3]

【補正対象書類名】明細書[Document name to be amended] Statement

【補正対象項目名】００５８[Correction target item name] 0058

【補正方法】変更[Correction method] Change

【補正内容】[Correction contents]

【００５８】本実施形態の接合法によれば、各熱電半導
体１，２中にＳｎが拡散しやすくので、Ｓｎ膜４００と
各熱電半導体１，２との接合強度が向上する。ここに、
熱電半導体１，２中にＳｎが拡散されたことによる熱電
半導体１，２の性能劣化や経時劣化は小さく、熱電変換
モジュールの熱電性能の信頼性を損なうことはない。According to the bonding method of this embodiment , each thermoelectric semiconductor
Since Sn is easily diffused into the bodies 1 and 2, the bonding strength between the Sn film 400 and each of the thermoelectric semiconductors 1 and 2 is improved. here,
The performance deterioration and the deterioration over time of the thermoelectric semiconductors 1 and 2 due to the diffusion of Sn into the thermoelectric semiconductors 1 and 2 are small, and the reliability of the thermoelectric performance of the thermoelectric conversion module is not impaired.

【手続補正４】[Procedure amendment 4]

【補正対象書類名】明細書[Document name to be amended] Statement

【補正対象項目名】００６６[Correction target item name] 0066

【補正方法】変更[Correction method] Change

【補正内容】[Correction contents]

【００６６】本実施形態では、 図１０（ａ）に示すよ
うな小ブロック体５の導電性接合部材３の一部を除去し
て図１０（ｄ）に示すような複数の電極６を形成するに
は、図１０（ａ）に示すような複数の電極６を形成する
には、まず図１０（ｂ）に示すように小ブロック体５の
正面（図１０（ｂ）の紙面表側）に、除去部以外を覆う
ような（除去部に対応する部位に開口部５８ａを有す
る）金属製マスク５８を設け、サンドブラストを行うこ
とにより各導電性接合部材３の一部を除去して電極６を
形成する。その後、金属製マスク５８を取り除くことに
より、図１０（ｃ）に示すような所望の電極６を有する
熱電変換モジュール１００が得られる。In this embodiment, a plurality of electrodes 6 as shown in FIG. 10D are formed by removing a part of the conductive bonding member 3 of the small block body 5 as shown in FIG. 10A. In order to form a plurality of electrodes 6 as shown in FIG. 10 (a), first, as shown in FIG. 10 (b) , An electrode 6 is formed by providing a metal mask 58 that covers portions other than the removed portion (having an opening 58a at a portion corresponding to the removed portion) and performing a sandblast to remove a part of each conductive bonding member 3. I do. Thereafter, by removing the metal mask 58, a thermoelectric conversion module 100 having desired electrodes 6 as shown in FIG. 10C is obtained.

【手続補正５】[Procedure amendment 5]

【補正対象書類名】明細書[Document name to be amended] Statement

【補正対象項目名】００６８[Correction target item name]

【補正方法】変更[Correction method] Change

【補正内容】[Correction contents]

【００６８】ところで、上記実施形態でｐ形熱電半導体
１の主材料である（Ｓｂ，Ｂｉ） 2Ｔｅ3 系化合物半導
体の結晶及びｎ形熱電半導体２の主材料であるＢｉ
2 （Ｔｅ，Ｓｅ）3 系化合物半導体の結晶は菱面体構造
をもつ層状化合物であり、その結晶対称性から熱電気輸
送現象に大きな異方性を示す（大きな異方性を有するの
で、通電方向により導電率に大きな違いが生じる）。こ
の単結晶のｃ軸に垂直な方向（つまり、ｃ面に平行な方
向）は、ｃ軸に平行な方向よりも導電率が大きいので熱
電性能指数Ｚが大きく、またａ軸方向が結晶の成長方向
であるため実用には一方向凝固によって成長方向にａ軸
をそろえた大きな結晶粒からなる多結晶材料が使用され
ている。なお、ｃ面に平行な方向への結晶構造がイオン
結合と共有結合とで構成されているのに対し、ｃ面に垂
直な方向（ｃ軸方向）へは分子間結合が含まれているの
で、ｃ軸方向への導電率が減少する。In the above embodiment, the crystal of the (Sb, Bi) 2 Te 3 -based compound semiconductor which is the main material of the p-type thermoelectric semiconductor 1 and the Bi which is the main material of the n-type thermoelectric semiconductor 2
The crystal of the 2 (Te, Se) 3 -based compound semiconductor is a layered compound having a rhombohedral structure, and exhibits a large anisotropy in thermoelectric transport phenomena due to its crystal symmetry. Causes a large difference in conductivity). The direction perpendicular to the c-axis of this single crystal (that is, the direction parallel to the c-plane) is higher in conductivity than the direction parallel to the c-axis, so the thermoelectric figure of merit Z is larger, and the a-axis direction is crystal growth. Because of the direction, a polycrystalline material composed of large crystal grains whose a-axis is aligned in the growth direction by unidirectional solidification is practically used. Since the crystal structure in the direction parallel to the c-plane is composed of ionic bonds and covalent bonds, the intermolecular bond is included in the direction perpendicular to the c-plane (c-axis direction). , C-axis direction decreases.

【手続補正６】[Procedure amendment 6]

【補正対象書類名】明細書[Document name to be amended] Statement

【補正対象項目名】００７０[Correction target item name] 0070

【補正方法】変更[Correction method] Change

【補正内容】[Correction contents]

【００７０】しかして、本実施形態では、各熱電半導体
１，２の熱電性能指数Ｚが高く得られる方向と熱電変換
モジュール１００を構成した場合における各熱電半導体
１，２の通電方向とを一致させてあるので、熱電変換モ
ジュール１００の熱電性能を向上させることができる。
なお、（Ｓｂ，Ｂｉ） 2 Ｔｅ3 系化合物半導体、Ｂｉ2
（Ｔｅ，Ｓｅ）3 系化合物半導体の熱電特性は、焼結に
より形成される場合にも単結晶に類似の異方性を有し、
焼結前のプレス方向が単結晶のｃ軸に対応するので、焼
結により形成される熱電半導体を用いた場合にも、ｃ面
に相当する面に平行な面が上記通電方向に対して平行と
なる。In this embodiment, the direction in which the thermoelectric performance index Z of each of the thermoelectric semiconductors 1 and 2 is obtained is made to match the direction in which the thermoelectric semiconductors 1 and 2 are energized when the thermoelectric conversion module 100 is constructed. Therefore, the thermoelectric performance of the thermoelectric conversion module 100 can be improved.
In addition, (Sb, Bi) 2 Te 3 -based compound semiconductor, Bi 2
The thermoelectric properties of the (Te, Se) 3 -based compound semiconductor have anisotropy similar to that of a single crystal even when formed by sintering,
Since the pressing direction before sintering corresponds to the c-axis of the single crystal, even when using a thermoelectric semiconductor formed by sintering, the plane parallel to the plane corresponding to the c-plane is parallel to the energizing direction. Becomes

【手続補正７】[Procedure amendment 7]

【補正対象書類名】明細書[Document name to be amended] Statement

【補正対象項目名】００７３[Correction target item name] 0073

【補正方法】変更[Correction method] Change

【補正内容】[Correction contents]

【００７３】なお、熱電変換モジュール１００’の上面
及び下面に露出すべき電極６の表面に絶縁性材料１１２
が付着したり、あるいは、絶縁性材料１１２の過不足そ
の他により、熱電変換モジュール１００’の放熱面（例
えば上記上面）や吸着面（上記下面）の平坦度が損なわ
れた不良品が万一発生したときは、薬液で清浄したりあ
るいは機械的研磨により所望の平坦度が得られるように
加工すればよい。The surface of the electrode 6 to be exposed on the upper and lower surfaces of the thermoelectric conversion module 100 ′ is coated with an insulating material 112.
The flatness of the heat radiating surface (for example, the upper surface) and the suction surface (the lower surface) of the thermoelectric conversion module 100 ′ is deteriorated due to the adhesion of the insulating material 112, excess or deficiency of the insulating material 112, and the like.
In the event that a defective product occurs, it may be cleaned by a chemical solution or mechanically polished to obtain a desired flatness.

【手続補正８】[Procedure amendment 8]

【補正対象書類名】明細書[Document name to be amended] Statement

【補正対象項目名】００７６[Correction target item name] 0076

【補正方法】変更[Correction method] Change

【補正内容】[Correction contents]

【００７６】なお、熱電変換モジュール１００’の上面
及び下面に露出すべき電極６の表面に絶縁性材料１１３
が付着したり、あるいは、絶縁性材料１１３の過不足そ
の他により、熱電変換モジュール１００’の放熱面（例
えば上記上面）や吸着面（上記下面）の平坦度が損なわ
れた不良品が万一発生したときは、薬液で清浄したりあ
るいは機械的研磨により所望の平坦度が得られるように
加工すればよい。The surface of the electrode 6 to be exposed on the upper and lower surfaces of the thermoelectric conversion module 100 ′ has an insulating material 113.
The flatness of the heat radiating surface (for example, the upper surface) or the suction surface (the lower surface) of the thermoelectric conversion module 100 ′ is impaired due to the adhesion of the insulating material 113, the excess or deficiency of the insulating material 113, and the like.
In the event that a defective product occurs, it may be cleaned by a chemical solution or mechanically polished to obtain a desired flatness.

【手続補正９】[Procedure amendment 9]

【補正対象書類名】明細書[Document name to be amended] Statement

【補正対象項目名】００７９[Correction target item name] 0079

【補正方法】変更[Correction method] Change

【補正内容】[Correction contents]

【００７９】なお、熱電変換モジュール１００’の上面
及び下面に露出すべき電極６の表面に絶縁性材料１１４
が付着したり、あるいは、絶縁性材料１１４の過不足そ
の他により、熱電変換モジュール１００’の放熱面（例
えば上記上面）や吸着面（上記下面）の平坦度が損なわ
れた不良品が万一発生したときは、薬液で清浄したりあ
るいは機械的研磨により所望の平坦度が得られるように
加工すればよい。The surface of the electrode 6 to be exposed on the upper and lower surfaces of the thermoelectric conversion module 100 ′ is coated with an insulating material 114.
The flatness of the heat radiating surface (for example, the upper surface) and the suction surface (the lower surface) of the thermoelectric conversion module 100 ′ is impaired due to adhesion of the insulating material 114, excess or deficiency of the insulating material 114, and the like.
In the event that a defective product occurs, it may be cleaned by a chemical solution or mechanically polished to obtain a desired flatness.

【手続補正１０】[Procedure amendment 10]

【補正対象書類名】明細書[Document name to be amended] Statement

【補正対象項目名】００８１[Correction target item name] 0081

【補正方法】変更[Correction method] Change

【補正内容】[Correction contents]

【００８１】なお、熱電変換モジュール１００’の上面
及び下面に露出すべき電極６の表面に絶縁性材料１１５
が付着したり、あるいは、絶縁性材料１１５の過不足そ
の他により、熱電変換モジュール１００’の放熱面（例
えば上記上面）や吸着面（上記下面）の平坦度が損なわ
れた不良品が万一発生したときは、薬液で清浄したりあ
るいは機械的研磨により所望の平坦度が得られるように
加工すればよい。The surface of the electrode 6 to be exposed on the upper and lower surfaces of the thermoelectric conversion module 100 ′ is coated with an insulating material 115.
The flatness of the heat radiating surface (for example, the upper surface) and the suction surface (the lower surface) of the thermoelectric conversion module 100 ′ are deteriorated due to the adhesion of the insulating material 115 or the excess or deficiency of the insulating material 115.
In the event that a defective product occurs, it may be cleaned by a chemical solution or mechanically polished to obtain a desired flatness.

───────────────────────────────────────────────────── フロントページの続き (72)発明者 小林 健太郎 大阪府門真市大字門真1048番地松下電工株 式会社内 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Kentaro Kobayashi 1048 Odakadoma, Kadoma City, Osaka Prefecture Matsushita Electric Works, Ltd.

Claims (27)

【特許請求の範囲】[Claims] 【請求項１】 ｐ形熱電半導体とｎ形熱電半導体とが電
極を介して同一方向に交互に配設されるとともに接合さ
れ、かつ上記電極が該配設方向に直交する厚み方向の両
端側に交互に設けられる熱電変換モジュールの製造方法
であって、ｐ形熱電半導体とｎ形熱電半導体との間に導
電性接合部材を設けて接合し一体化することによりブロ
ック体を形成する第１の工程と、上記ブロック体を各熱
電半導体と導電性接合部材との接合面に対して略直交す
るように切断することにより所望の厚さの小ブロック体
を形成する第２の工程と、小ブロック体の厚み方向の一
端側と他端側とから交互に導電性接合部材の一部を除去
することにより導電性接合部材よりなる上記電極を形成
する第３の工程とを有することを特徴とする熱電変換モ
ジュールの製造方法。1. A p-type thermoelectric semiconductor and an n-type thermoelectric semiconductor are alternately arranged and joined in the same direction via electrodes, and the electrodes are provided at both ends in a thickness direction orthogonal to the arrangement direction. A method of manufacturing a thermoelectric conversion module provided alternately, wherein a first step of forming a block body by providing a conductive joining member between a p-type thermoelectric semiconductor and an n-type thermoelectric semiconductor and joining and integrating them. And a second step of forming the small block body having a desired thickness by cutting the block body so as to be substantially orthogonal to the bonding surface between each thermoelectric semiconductor and the conductive bonding member; A third step of alternately removing a portion of the conductive bonding member from one end side and the other end side in the thickness direction to form the electrode made of the conductive bonding member. Manufacturing method of conversion module . 【請求項２】 導電性接合部材として各熱電半導体と同
程度の線膨張率及び変形抵抗を有する金属を用い、導電
性接合部材と各熱電半導体とを押し出し加工により接合
することをことを特徴とする請求項１記載の熱電変換モ
ジュールの製造方法。2. The method according to claim 1, wherein a metal having the same linear expansion coefficient and deformation resistance as each thermoelectric semiconductor is used as the conductive bonding member, and the conductive bonding member and each thermoelectric semiconductor are bonded by extrusion. The method for manufacturing a thermoelectric conversion module according to claim 1. 【請求項３】 導電性接合部材を内部に複数の収納室が
一方向に列設されたカプセルとし、ｐ形熱電半導体粉末
とｎ形熱電半導体粉末とをカプセルの所定の収納室に充
填した後に、押し出し加工を行うことにより導電性接合
部材と各熱電半導体とを接合することを特徴とする請求
項２記載の熱電変換モジュールの製造方法。3. A capsule in which a plurality of storage chambers are arranged in one direction in a conductive bonding member, and p-type thermoelectric semiconductor powder and n-type thermoelectric semiconductor powder are filled in a predetermined storage chamber of the capsule. 3. The method for manufacturing a thermoelectric conversion module according to claim 2, wherein the conductive joining member and each thermoelectric semiconductor are joined by extruding. 【請求項４】 導電性接合部材を内部に複数の収納室が
一方向に列設されたカプセルとし、ｐ形熱電半導体圧粉
体とｎ形熱電半導体圧粉体とをカプセルの所定の収納室
に充填した後に、押し出し加工を行うことにより導電性
接合部材と各熱電半導体とを接合することを特徴とする
請求項２記載の熱電変換モジュールの製造方法。4. A capsule in which a plurality of storage chambers are arranged in one direction in a conductive joining member, and a p-type thermoelectric semiconductor compact and an n-type thermoelectric semiconductor compact are stored in a predetermined storage chamber of the capsule. 3. The method for manufacturing a thermoelectric conversion module according to claim 2, wherein the conductive bonding member and each thermoelectric semiconductor are bonded by extruding after filling. 【請求項５】 押し出し加工後に、押し出された押し出
し部材を焼結することを特徴とする請求項３又は請求項
４記載の熱電変換モジュールの製造方法。5. The method for manufacturing a thermoelectric conversion module according to claim 3, wherein the extruded extruded member is sintered after the extruding process. 【請求項６】 導電性接合部材として各熱電半導体と同
程度の弾性率を有する金属を用い、各熱電半導体として
熱電半導体粉末を用い、ホットプレスにより各熱電半導
体と導電性接合部材とを接合することを特徴とする請求
項１記載の熱電変換モジュールの製造方法。6. A metal having substantially the same elastic modulus as each thermoelectric semiconductor is used as a conductive bonding member, a thermoelectric semiconductor powder is used as each thermoelectric semiconductor, and each thermoelectric semiconductor and the conductive bonding member are bonded by hot pressing. The method for manufacturing a thermoelectric conversion module according to claim 1, wherein: 【請求項７】 導電性接合部材として各熱電半導体と同
程度の弾性率を有する金属を用い、各熱電半導体として
熱電半導体粉末を用い、熱間静水圧プレスにより各熱電
半導体と導電性接合部材とを接合することを特徴とする
請求項１記載の熱電変換モジュールの製造方法。7. A metal having the same elastic modulus as each thermoelectric semiconductor as a conductive bonding member, a thermoelectric semiconductor powder as each thermoelectric semiconductor, and each thermoelectric semiconductor and the conductive bonding member are subjected to hot isostatic pressing. The method for manufacturing a thermoelectric conversion module according to claim 1, wherein 【請求項８】 各熱電半導体と導電性接合部材との間
に、導電性を有し且つ各熱電半導体へ拡散可能であって
該拡散による各熱電半導体の性能劣化の少ない導電性中
間部材を介在させてブロック体を形成することを特徴と
する請求項１記載の熱電変換モジュールの製造方法。8. A conductive intermediate member having conductivity and capable of being diffused to each thermoelectric semiconductor and having little performance deterioration of each thermoelectric semiconductor due to the diffusion is interposed between each thermoelectric semiconductor and the conductive bonding member. The method for manufacturing a thermoelectric conversion module according to claim 1, wherein the block body is formed by causing the block body to be formed. 【請求項９】 各熱電半導体と導電性接合部材との間
に、導電性を有し且つ他の部材からの拡散を防止する拡
散防止部材を介在させてブロック体を形成することを特
徴とする請求項１又は請求項８記載の熱電変換モジュー
ルの製造方法。9. A block body is formed between each thermoelectric semiconductor and the conductive bonding member by interposing a diffusion preventing member having conductivity and preventing diffusion from other members. A method for manufacturing a thermoelectric conversion module according to claim 1. 【請求項１０】 各熱電半導体と導電性接合部材との間
に、高い延性を有する導電性中間部材を介在させて押し
出し加工を行うことを特徴とする請求項２記載の熱電変
換モジュールの製造方法。10. The method for manufacturing a thermoelectric conversion module according to claim 2, wherein extrusion is performed by interposing a conductive intermediate member having high ductility between each thermoelectric semiconductor and the conductive bonding member. . 【請求項１１】 導電性接合部材及び熱電半導体の少な
くとも一方の表面を、機械的切削、化学エッチング、サ
ンドブラストなどにより粗面化した後に、各熱電半導体
と導電性接合部材とを接合することを特徴とする請求項
１記載の熱電変換モジュールの製造方法。11. The method according to claim 1, wherein at least one surface of the conductive bonding member and the thermoelectric semiconductor is roughened by mechanical cutting, chemical etching, sandblasting or the like, and then each thermoelectric semiconductor and the conductive bonding member are bonded. The method for manufacturing a thermoelectric conversion module according to claim 1. 【請求項１２】 導電性中間部材を容器状にし、該容器
状に形成された導電性中間層材に熱電半導体を充填した
後にブロック体を形成することを特徴とする請求項８又
は請求項１０記載の熱電変換モジュールの製造方法。12. The conductive intermediate member is formed in a container shape, and a block body is formed after filling a thermoelectric semiconductor into a conductive intermediate layer material formed in the container shape. A manufacturing method of the thermoelectric conversion module according to the above. 【請求項１３】 ブロック体を形成する前に、導電性接
合部材の表面に、メッキ、スパッタリング、ペースト塗
布等のいずれかの方法により導電性中間部材を形成する
工程を有することを特徴とする請求項８又は請求項１０
又は請求項１１記載の熱電変換モジュールの製造方法。13. The method according to claim 1, further comprising a step of forming a conductive intermediate member on the surface of the conductive bonding member by any one of plating, sputtering, and paste application before forming the block body. Claim 8 or Claim 10
A method for manufacturing a thermoelectric conversion module according to claim 11. 【請求項１４】 ブロック体を形成する前に、各熱電半
導体の表面に、メッキ、スパッタリング、ペースト塗布
等のいずれかの方法により導電性中間部材を形成する工
程を有することを特徴とする請求項８又は請求項１０又
は請求項１１記載の熱電変換モジュールの製造方法。14. The method according to claim 1, further comprising a step of forming a conductive intermediate member on the surface of each thermoelectric semiconductor by any one of plating, sputtering, and paste application before forming the block body. A method for manufacturing a thermoelectric conversion module according to claim 8 or claim 10. 【請求項１５】 上記第３の工程は、導電性接合部材の
一部をダイシングソーなどを用いた機械加工により除去
することを特徴とする請求項１記載の熱電変換モジュー
ルの製造方法。15. The method of manufacturing a thermoelectric conversion module according to claim 1, wherein in the third step, a part of the conductive bonding member is removed by machining using a dicing saw or the like. 【請求項１６】 上記第３の工程は、導電性接合部材の
一部をレーザにより除去することを特徴とする請求項１
記載の熱電変換モジュールの製造方法。16. The method according to claim 1, wherein the third step removes a part of the conductive bonding member by using a laser.
A manufacturing method of the thermoelectric conversion module according to the above. 【請求項１７】 上記第３の工程は、小ブロック体を導
電性接合部材の除去部が開孔されたマスクを設けた後
に、サンドブラストにより導電性接合部材の一部を除去
することを特徴とする請求項１記載の熱電変換モジュー
ルの製造方法。17. The third step is characterized in that a small block body is provided with a mask in which a portion for removing the conductive bonding member is opened, and then a part of the conductive bonding member is removed by sandblasting. The method for manufacturing a thermoelectric conversion module according to claim 1. 【請求項１８】 熱電変換モジュールへの通電時に各熱
電半導体の結晶面が通電方向に対して平行に配向するよ
うに各熱電半導体を形成することを特徴とする請求項１
記載の熱電変換モジュールの製造方法。18. The thermoelectric semiconductor according to claim 1, wherein each thermoelectric semiconductor is formed such that a crystal plane of each thermoelectric semiconductor is oriented in parallel to a direction of current when power is supplied to the thermoelectric conversion module.
A manufacturing method of the thermoelectric conversion module according to the above. 【請求項１９】 導電性接合部材が除去された除去部を
樹脂などの絶縁性材料で充填することを特徴とする請求
項１記載の熱電変換モジュールの製造方法。19. The method for manufacturing a thermoelectric conversion module according to claim 1, wherein the removed portion from which the conductive bonding member has been removed is filled with an insulating material such as a resin. 【請求項２０】 絶縁性材料として熱伝導率が略０．０
１Ｗ／ｍＫ乃至略０．５Ｗ／ｍＫの低熱伝導率材料を使
用することを特徴とする請求項１９記載の熱電変換モジ
ュールの製造方法。20. An insulating material having a thermal conductivity of about 0.0
The method for manufacturing a thermoelectric conversion module according to claim 19, wherein a low thermal conductivity material of 1 W / mK to about 0.5 W / mK is used. 【請求項２１】 絶縁性材料としてシリコーン樹脂のよ
うな柔軟性のある材料を使用することを特徴とする請求
項１９記載の熱電変換モジュールの製造方法。21. The method according to claim 19, wherein a flexible material such as a silicone resin is used as the insulating material. 【請求項２２】 絶縁性材料としてエポキシ樹脂のよう
な熱電半導体との接合強度が熱電半導体の引っ張り強度
以上の高接着性樹脂を使用することを特徴とする請求項
１９記載の熱電変換モジュールの製造方法。22. The manufacturing of a thermoelectric conversion module according to claim 19, wherein the insulating material is a highly adhesive resin such as an epoxy resin, the bonding strength of which is higher than the tensile strength of the thermoelectric semiconductor. Method. 【請求項２３】 絶縁性材料として３００℃以上の耐熱
性を有するエポキシ樹脂やポリイミド樹脂のような高耐
熱性材料を使用することを特徴とする請求項１９記載の
熱電変換モジュールの製造方法。23. The method for manufacturing a thermoelectric conversion module according to claim 19, wherein a high heat resistant material such as an epoxy resin or a polyimide resin having a heat resistance of 300 ° C. or more is used as the insulating material. 【請求項２４】 上記除去部を絶縁性材料で充填する前
に、化学的エッチング、サンドブラスト等により各熱電
半導体の表面を粗面化することを特徴とする請求項１９
乃至請求項２３記載の熱電変換モジュールの製造方法。24. The thermoelectric semiconductor according to claim 19, wherein the surface of each thermoelectric semiconductor is roughened by chemical etching, sandblasting or the like before filling the removed portion with an insulating material.
24. The method for manufacturing a thermoelectric conversion module according to claim 23. 【請求項２５】 上記第１、第２、第３の工程により形
成された熱電変換モジュールの厚み方向の両面における
電極及び各熱電半導体の表面に熱伝導率の高い金属薄膜
を形成する工程を有することを特徴とする請求項１又は
請求項１９記載の熱電変換モジュールの製造方法。25. A step of forming a metal thin film having high thermal conductivity on the surface of each of the electrodes and the thermoelectric semiconductors on both sides in the thickness direction of the thermoelectric conversion module formed by the first, second, and third steps. The method for manufacturing a thermoelectric conversion module according to claim 1 or claim 19, wherein: 【請求項２６】 上記第１、第２、第３の工程により形
成された熱電変換モジュールの厚み方向の両面における
電極及び各熱電半導体の表面に導電性薄膜を形成もしく
は導電性薄板を接合する工程を有することを特徴とする
請求項１又は請求項１９記載の熱電変換モジュールの製
造方法。26. A step of forming a conductive thin film or bonding a conductive thin plate on the surface of each of the electrodes and thermoelectric semiconductors on both sides in the thickness direction of the thermoelectric conversion module formed by the first, second, and third steps. The method for manufacturing a thermoelectric conversion module according to claim 1 or 19, comprising: 【請求項２７】 上記第１、第２、第３の工程により形
成された熱電変換モジュールの全面に樹脂等の絶縁性材
料をコーティングする工程を有することを特徴とする請
求項１又は請求項１９又は請求項２５又は請求項２６記
載の熱電変換モジュールの製造方法。27. The method according to claim 1, further comprising a step of coating an insulating material such as a resin on the entire surface of the thermoelectric conversion module formed in the first, second, and third steps. 27. A method for manufacturing a thermoelectric conversion module according to claim 25.
JP22869397A 1997-08-26 1997-08-26 Method for manufacturing thermoelectric conversion module Expired - Fee Related JP3724133B2 (en)

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