JP2004140064A - Thermoelement and its manufacturing method - Google Patents

Thermoelement and its manufacturing method Download PDF

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Publication number
JP2004140064A
JP2004140064A JP2002301534A JP2002301534A JP2004140064A JP 2004140064 A JP2004140064 A JP 2004140064A JP 2002301534 A JP2002301534 A JP 2002301534A JP 2002301534 A JP2002301534 A JP 2002301534A JP 2004140064 A JP2004140064 A JP 2004140064A
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metal
thermoelectric
insulating layer
thermoelectric element
thermoelement
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JP4199513B2 (en
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Tetsuhiro Nakamura
中村　　哲浩
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Citizen Watch Co Ltd
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Citizen Watch Co Ltd
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Abstract

<P>PROBLEM TO BE SOLVED: To solve the problems wherein a conductive material is liable to separate from a thermoelectric semiconductor due to a thermal expansion coefficient difference between a heat dissipating board and a thermoelement because metal interconnect lines formed on the heat dissipating board are electrically connected to the thermoelectric semiconductor provided with a conductive material formed on its front surface with solder or a conductive adhesive agent in a thermoelement having a conventional structure, the thermoelement can not be set high enough in reliability and performance because an electrical connection is liable to be often disconnected in a heat cycle test, and the thermoelement is restrained from being reduced in size due to the fact that the thickness of the heat dissipating board causes increase in the thickness of the whole thermoelement. <P>SOLUTION: The p-type thermoelements and the n-type thermoelements are alternately arranged through the intermediary of an insulator. The thermoelements are electrically connected together with metal members and metal interconnect lines, the surfaces of the metal interconnect lines and the insulators are protected by an insulating layer containing thermally conductive particles and catalytic metal particles, and a metal layer is formed on the surface of the insulating layer. <P>COPYRIGHT: (C)2004,JPO

Description

【０００１】
【発明の属する技術分野】
本発明は熱電素子の構造およびその製造方法に関するものである。
【０００２】
【従来の技術】
以下、図面を用いて従来技術の一例を説明する。図１６は従来例の熱電素子の構造を示す断面図である（たとえば、非特許文献１参照。）。図１６に示すようにｐ型とｎ型の熱電半導体１を交互に配置し、熱電半導体１の両端部に導電材１８を設けた熱電半導体１と、放熱板１７上に形成した銅や金などからなる金属配線４とを、ハンダ１６を用いて電気的に接続している。
【０００３】
この図１６に示す熱電素子は、上下面で温度差がある場合には発電素子として使用することができ、熱電素子に電流を流すと上下面の一方が発熱し、一方が吸熱するため、冷却用または加熱用素子として使用することができる。
【０００４】
熱電半導体としては、一般的に用いられるビスマス−テルル系、アンチモン−テルル系、ビスマス−テルル−アンチモン系、ビスマス−テルル−セレン系の他に、鉛−ゲルマニウム系、シリコン−ゲルマニウム系などの材料が用いられる。
【０００５】
次に従来例における熱電素子の製造方法を図１２から図１６を用いて説明する。まず、ｐ型、ｎ型の熱電半導体１のそれぞれの表面に図１２に示すように導電材１８とハンダ１６を電解メッキにより形成する。
【０００６】
熱電半導体１と金属配線４を電気的に接続させる接続材料としてハンダ１６を用いた場合、ハンダ中のスズ成分が熱電半導体１内に拡散して性能を劣化させるのを防止する目的と、ハンダの濡れ性を確保する目的で熱電半導体１の表面には導電材１８を形成している。導電材１８としては、熱電半導体１への金属拡散防止効果の高いニッケルが主に形成される。
【０００７】
導電材１８とハンダ１６を形成した熱電半導体１をダイシングソーやワイヤーソーなどで切断し、図１３に示すような柱状の熱電半導体１を形成する。
【０００８】
金属配線４を形成した放熱板１７上にフラックス１９を塗布し、図１３に示す導電材１８とハンダ１６が形成された柱状の熱電半導体１を図１４に示すようにｐ型とｎ型の熱電半導体１が交互になるように配置する。
【０００９】
さらにもう一方の金属配線４を形成した放熱板１７をフラックス１９を介して図１５に示すように配置し、熱電半導体１を放熱板１７で挟んだ後、熱処理によって熱電半導体１上に形成された導電材１８と放熱板１７上に形成された金属配線４とをハンダ１６により接合し、フラックス１９を洗浄し除去することにより図１６に示すような熱電素子を得ることができる。
放熱板１７としてはシリコン、アルミナなどの熱伝導の良い材料を用いる。金属配線４としては、メッキ法、スパッタリング法、真空蒸着法などにより形成された銅やニッケルや金などの皮膜をエッチングなどによりパターン化したものを使用している。
【００１０】
【非特許文献１】
上村欣一・西田勲夫著「熱電半導体とその応用」日刊工業新聞社、１９８８年１２月２０日、ｐ．３９−４１
【００１１】
【発明が解決しようとする課題】
前述した熱電素子には以下に記載するような問題点がある。
【００１２】
従来の熱電素子の構造では、放熱板１７上に形成した金属配線４と端面に導電材１８を設けた熱電半導体１とをハンダ１６を用いて電気的に接続しているが、熱電素子が熱膨張または熱収縮することにより、導電材１８と熱電半導体１との間で剥離が発生し、ｐ型とｎ型の熱電半導体１の電気的接続が断線してしまう。電気的接続の断線は加熱と冷却を交互に繰り返す温度サイクル試験で顕著に現れ、信頼性の面でも十分な性能を得られていない。
【００１３】
また、放熱板１７として厚さが０．５ｍｍ程度のアルミナを使用しているが、放熱板１７の厚みが熱電素子全体の厚みを増加させてしまうことになり、熱電素子を小型化する際の大きな問題点となっている。
【００１４】
本発明の目的は、上記課題を解決して、小型でかつ信頼性の高い熱電素子およびその製造方法を提供することにある。
【００１５】
【課題を解決するための手段】
上記の目的を達成するために、本発明における熱電素子およびその製造方法は、下記記載の構成と製造方法を採用する。
【００１６】
本発明の熱電素子は、ｐ型とｎ型の複数の熱電半導体を絶縁物を介して交互に配列し、前記熱電半導体が金属部材および金属配線によって電気的に直列に接続した熱電素子において、前記金属配線および前記絶縁物上に熱伝導粒子と触媒金属粒子とを含有した絶縁層を形成しており、絶縁層上に金属層が形成されていることを特徴としている。
【００１７】
本発明の熱電素子の製造方法は、絶縁物を介して配列している複数のｐ型とｎ型の熱電半導体を用意する工程と、前記熱電半導体を電気的に直列に接続するための土台となる金属部材を形成する工程と、前記金属部材上と前記金属部材が形成されていない前記熱電半導体の端部面とに金属配線を形成する工程と、前記金属配線および前記絶縁物表面に絶縁層を形成する工程と、前記絶縁層表面に金属層を形成する工程とを有することを特徴としている。
【００１８】
［作用］
本発明の熱電素子は、ｐ型とｎ型の複数の熱電半導体を絶縁物を介して交互に配列し、各熱電半導体１が金属部材および金属配線によって電気的に接続され、金属配線および絶縁物表面を熱伝導粒子と触媒金属粒子とを含有した絶縁層によって保護しており、絶縁層の表面に金属層が形成されている構造となっている。
【００１９】
このように複数の熱電半導体を電気的に接続している金属配線と絶縁物表面に熱伝導粒子と触媒金属粒子とを含有した絶縁層を形成することにより、金属配線を絶縁、保護し、金属配線の剥離を防止する補強効果を得ることができる。
【００２０】
また、絶縁層には熱伝導粒子と触媒金属粒子とを含有しているので、熱電素子を加熱または冷却した場合の被冷却物や被加熱物に伝わる熱の損失を少なくすることができ、触媒金属粒子を含有しているので、触媒金属粒子を核として絶縁層上に金属層を無電解メッキ法により形成することができ、被冷却物や被加熱物をハンダを用いて金属層に接合することができる。
【００２１】
これにより、従来の熱電素子で使用していた放熱板を用いずに熱電素子を形成することができ、小型で信頼性の高い熱電素子を得ることができる。
【００２２】
【発明の実施の形態】
以下図面を用いて本発明の最適な実施形態における熱電素子について説明する。図１に本実施形態における熱電素子の断面図を示す。図１に示すように、ｐ型とｎ型の複数の熱電半導体１を絶縁物２を介して交互に配列し、各熱電半導体１を金属部材３および金属配線４によって電気的に接続し、金属配線４および絶縁物２表面を熱伝導粒子１０と触媒金属粒子１１とを含有した絶縁層５によって保護しており、絶縁層５の表面に金属層６が形成されている構造となっている。
【００２３】
金属部材３はｐ型とｎ型の熱電半導体１が電気的に直列接続する部分に配置しており、熱電半導体１上と熱電半導体１間の絶縁物２上をまたぐように形成している。これにより金属配線４を電解メッキまたは無電解メッキにより金属部材３上および熱電半導体１上に形成すると同時に、ｐ型とｎ型の熱電半導体１を電気的に直列接続することができる。
【００２４】
また、複数の熱電半導体１を電気的に接続している金属配線４と絶縁物２表面に熱伝導粒子１０と触媒金属粒子１１とを含有した絶縁層５を形成することにより、金属配線４を絶縁、保護し、金属配線４の剥離を防止する補強効果を得ることができる。
【００２５】
絶縁層５には熱伝導粒子１０と触媒金属粒子１１とを含有しているので、熱電素子を加熱または冷却した場合の被冷却物や被加熱物に伝わる熱の損失を少なくすることができ、触媒金属粒子１１を含有しているので、触媒金属粒子１１を核として絶縁層５上に金属層６を無電解メッキ法により形成することができ、被冷却物や被加熱物をハンダ１６を用いて金属層６に接合することができる。
【００２６】
これにより、従来の熱電素子で使用していた放熱板１７を用いずに熱電素子を形成することができ、小型で信頼性の高い熱電素子を得ることができる。
【００２７】
次に、本実施形態における熱電素子の製造方法について図１から図１２を用いて説明する。まず、５０ｍｍ×５０ｍｍ×５ｍｍの大きさのｐ型とｎ型の熱電半導体１のそれぞれを図２に示すように、櫛歯状になるようにダイシングソーで幅０．６ｍｍの溝を１．１ｍｍピッチで加工する。その後、溝に絶縁物２としてスリーボンド（株）のエポキシ樹脂２２８０Ｃ（商品名）を６０℃に加熱しながら流し込み、図３に示すように櫛歯状のｐ型とｎ型の熱電半導体１を組み合わせ、１３０℃で１時間加熱することによりエポキシ樹脂を硬化させる。その後、不要な部分を研削により除去し、図４に示すような構造の熱電素子ブロックを得た。
【００２８】
熱電半導体１としては、一般的に用いられるビスマス−テルル系、アンチモン−テルル系、ビスマス−テルル−アンチモン系、ビスマス−テルル−セレン系などを用いることができるが、鉛−ゲルマニウム系、シリコン−ゲルマニウム系などの熱電半導体を用いることができる。
【００２９】
次にｐ型とｎ型の熱電半導体１を接続する金属部材３を形成する。金属部材３の形成方法は、まずｐ型とｎ型の複数の熱電半導体１を絶縁物２を介して交互に配列した熱電半導体ブロックに開口部を設けたメタルマスクを熱電半導体１と絶縁物２との表面に配置し、真空蒸着法やスパッタリング法で金属被膜を形成し、メタルマスクを除去することによりメタルマスクの開口部にのみ金属部材３が図５に示すように形成される。金属部材３を形成する位置はｐ型とｎ型の熱電半導体１が電気的に直列に接続する部分であり、熱電半導体１上と熱電半導体１間の絶縁物２上をまたぐように形成している。
【００３０】
金属部材３は金属配線４を無電解メッキで形成する場合には、無電解メッキを開始させる触媒としての役割と熱電半導体１間の絶縁物２上に無電解メッキを行うための土台としての役割を果たしている。そのため金属部材３としては周期表第ＶＩＩＩ属の金属のいずれかを形成する。また、金属配線４を電解メッキで形成する場合には、熱電半導体１間の絶縁物２上に電解メッキを行うための土台の役割のみを果たすので、金属の種類については特に制限されない。本実施形態では熱電半導体１への金属拡散防止効果の高いニッケルを厚さ０．１μｍで形成した。
【００３１】
その後、無電解ニッケルメッキ液に浸漬しするか、電解ニッケルメッキを行い、金属部材３上と熱電半導体１上に図６に示すように金属配線４を形成する。本実施形態では奥野製薬工業（株）の無電解ニッケルメッキ液トップケミアロイＢ−１（商品名）を用いて、液温６０℃で１０分間無電解ニッケルメッキを行い、ニッケルを１μｍの厚みで金属配線４を形成した。
【００３２】
金属配線４の抵抗を低減させるために金属配線４として形成したニッケル上に電解メッキにより銅を厚さ１０μｍで形成し、さらに銅表面の酸化防止を目的として金を厚さ１μｍで形成した。電解銅メッキについては日本エレクトロプレイティング・エンジニヤース（株）の電解銅メッキ液ミクロファブＣｕ２００（商品名）を用い、液温２５℃で電流密度３Ａ／ｄｍ２で１５分電解銅メッキを行い、金メッキについてはＮＥケムキャットの電解金メッキ液ＮＣＦ−５００（商品名）を用い、液温２５℃で電流密度０．８Ａ／ｄｍ２で２分間電解金メッキを行った。
【００３３】
次に、図７に示すように金属配線４および絶縁物２表面に絶縁層５を印刷法により塗布し、加熱することにより絶縁層５を硬化させるが、その際に熱電素子の電力供給部分に当たる配線電極４上には絶縁層５を配置しないようにする。このことによりワイヤーボンディングやハンダ接合により外部の端子と接合することが可能となる。
【００３４】
このとき形成する絶縁層５は、図８に示すようにベース基材１２中に熱伝導粒子１０と触媒金属粒子１１とを含有したものを用いている。ベース基材１２により金属配線４を絶縁、保護し、金属配線４の剥離を防止する補強効果を得ることができ、熱伝導粒子１０を含有していることにより、熱電素子を加熱または冷却した場合の被冷却物や被加熱物に伝わる熱の損失を少なくすることができ、触媒金属粒子１１を含有していることにより、触媒金属粒子１１を核として絶縁層５上に金属層６を無電解メッキ法により形成することができ、被冷却物や被加熱物をハンダ１６を用いて金属層６に接合することが可能となる。
【００３５】
本実施形態ではベース基材１２としてスリーボンド（株）のエポキシ樹脂２２８０Ｃ（商品名）を２０重量部、熱伝導粒子１０として平均粒子径が約１０μｍのアルミナ粒子を７５重量部、触媒金属粒子１１として平均粒子径が約３μｍのパラジウム粒子を５重量部混合したものを使用し、１３０℃で１時間加熱することによりベース基材１２を硬化させた。
【００３６】
ベース基材１２の種類についてはエポキシ系、アクリル系などの接着剤などを用いることができるが特に限定されるものではなく、熱伝導粒子１０についても絶縁層５の熱伝導性と絶縁性を両立する材質のものであればよく、アルミナや窒化アルミニウムの粒子などを使用すると効果的であるが、特に限定されるものではない。触媒金属粒子１１については無電解メッキが可能な金属であれば問題なく、具体的には元素周期表の第ＶＩＩＩ族の金属粒子を１種類もしくは複数種類混合したものを用いるか、第ＶＩＩＩ族以外の金属との合金粒子などを用いてもよい。また、熱伝導粒子１０と触媒金属粒子１１の粒子径や形状についても特に限定するものではない。
【００３７】
その後、図９に示すように無電解メッキ液に浸漬することにより、絶縁層５中の触媒金属粒子１１を核として無電解メッキが開始し、絶縁層５表面に金属層６を形成することができる。無電解メッキ液は奥野製薬工業（株）のトップケミアロイＢ−１（商品名）を使用し、液温６０℃で１０分間無電解ニッケルメッキを行い、厚みが約１μｍのニッケルを形成した後、奥野製薬工業（株）の無電解金メッキ液フラッシュゴールドＮＢを用いて液温９０℃で３０分間無電解金メッキを行い、厚みが約０．１μｍの金を形成した。
【００３８】
図１０に示す熱電素子の点線部分をダイシングソーやワイヤーソーなどで分割することにより図１に示すような熱電素子を得ることができる。
【００３９】
上記工程により得られた図１に示すような熱電素子は、図１１に示すように被冷却物１５と金属層６とをハンダ１６を用いて接合したり、電力供給部分に当たる金属配線４および絶縁層５上の金属層６とガラスや樹脂などで形成した基板１３上に形成した銅や金などからなる接合パターン１４とをハンダ１６を用いて接合することが可能となる。
【００４０】
以上の工程により形成した熱電素子は、ｐ型とｎ型の複数の熱電半導体１を絶縁物２を介して交互に配列し、各熱電半導体１が金属部材３および金属配線４によって電気的に接続し、金属配線４および絶縁物２表面を熱伝導粒子と触媒金属粒子とを含有した絶縁層５によって保護しており、絶縁層５の表面に金属層６が形成されている構造となっている。
【００４１】
このように複数の熱電半導体１を電気的に接続している金属配線４と絶縁物２表面に熱伝導粒子と触媒金属粒子とを含有した絶縁層５を形成することにより、金属配線４を絶縁、保護し、金属配線４の剥離を防止する補強効果を得ることができる。
【００４２】
また、絶縁層５には熱伝導粒子と触媒金属粒子とを含有しているので、熱電素子を加熱または冷却した場合の被冷却物や被加熱物に伝わる熱の損失を少なくすることができ、触媒金属粒子を含有しているので、触媒金属を核として絶縁層５上に金属層６を無電解メッキ法により形成することができ、被冷却物や被加熱物をハンダを用いて金属層６に接合することができる。
【００４３】
これにより、従来の熱電素子で使用していた放熱板１７を用いずに熱電素子を形成することができ、小型で信頼性の高い熱電素子を得ることができる。
【００４４】
【発明の効果】
以上の説明で明らかなように、本発明の熱電素子は、ｐ型とｎ型の複数の熱電半導体を絶縁物を介して交互に配列し、各熱電半導体が金属部材および金属配線によって電気的に接続し、金属配線および絶縁物表面を熱伝導粒子と触媒金属粒子とを含有した絶縁層によって保護しており、絶縁層の表面に金属層が形成されている構造となっている。
【００４５】
このように複数の熱電半導体を電気的に接続している金属配線と絶縁物表面に熱伝導粒子と触媒金属粒子とを含有した絶縁層を形成することにより、金属配線を絶縁、保護し、金属配線の剥離を防止する補強効果を得ることができる。
【００４６】
また、絶縁層には熱伝導粒子と触媒金属粒子とを含有しているので、熱電素子を加熱または冷却した場合の被冷却物や被加熱物に伝わる熱の損失を少なくすることができ、触媒金属粒子を含有しているので、触媒金属を核として絶縁層上に金属層を無電解メッキ法により形成することができ、被冷却物や被加熱物をハンダを用いて金属層６に接合することができる。
【００４７】
これにより、従来の熱電素子で使用していた放熱板を用いずに熱電素子を形成することができ、小型で信頼性の高い熱電素子を得ることができる。
【図面の簡単な説明】
【図１】本発明の実施形態における熱電素子を示す断面図である。
【図２】本発明の実施形態における熱電素子の製造方法を示す断面図である。
【図３】本発明の実施形態における熱電素子の製造方法を示す断面図である。
【図４】本発明の実施形態における熱電素子の製造方法を示す断面図である。
【図５】本発明の実施形態における熱電素子の製造方法を示す断面図である。
【図６】本発明の実施形態における熱電素子の製造方法を示す断面図である。
【図７】本発明の実施形態における熱電素子の製造方法を示す断面図である。
【図８】本発明の実施形態における熱電素子の製造方法を示す断面図である。
【図９】本発明の実施形態における熱電素子の製造方法を示す断面図である。
【図１０】本発明の実施形態における熱電素子の製造方法を示す断面図である。
【図１１】本発明の実施形態における熱電素子の構造を示す断面図である。
【図１２】従来例における熱電素子の製造方法を示す断面図である。
【図１３】従来例における熱電素子の熱半導体の斜視図である。
【図１４】従来例における熱電素子の製造方法を示す断面図である。
【図１５】従来例における熱電素子の製造方法を示す断面図である。
【図１６】従来例における熱電素子の構造を示す断面図である。
【符号の説明】
１　熱電半導体
２　絶縁物
３　金属部材
４　金属配線
５　絶縁層
６　金属層
１０　熱伝導粒子
１１　　触媒金属粒子
１２　　ベース基材
１３　　基板
１４　　接合パターン
１５　　被冷却物
１６　ハンダ
１７　放熱板
１８　導電材
１９　フラックス[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a thermoelectric element structure and a method for manufacturing the same.
[0002]
[Prior art]
Hereinafter, an example of the related art will be described with reference to the drawings. FIG. 16 is a cross-sectional view showing the structure of a conventional thermoelectric element (for example, see Non-Patent Document 1). As shown in FIG. 16, p-type and n-type thermoelectric semiconductors 1 are alternately arranged, and a thermoelectric semiconductor 1 in which conductive materials 18 are provided at both ends of the thermoelectric semiconductor 1 and copper, gold, or the like formed on a heat dissipation plate 17. Is electrically connected to the metal wiring 4 composed of
[0003]
The thermoelectric element shown in FIG. 16 can be used as a power generating element when there is a temperature difference between the upper and lower surfaces, and when an electric current is applied to the thermoelectric element, one of the upper and lower surfaces generates heat, and one of them absorbs heat. Or a heating element.
[0004]
Examples of the thermoelectric semiconductor include commonly used materials such as bismuth-tellurium, antimony-tellurium, bismuth-tellurium-antimony, bismuth-tellurium-selenium, lead-germanium, and silicon-germanium. Used.
[0005]
Next, a method for manufacturing a thermoelectric element in a conventional example will be described with reference to FIGS. First, as shown in FIG. 12, a conductive material 18 and solder 16 are formed on each surface of the p-type and n-type thermoelectric semiconductors 1 by electrolytic plating.
[0006]
When the solder 16 is used as a connection material for electrically connecting the thermoelectric semiconductor 1 and the metal wiring 4, the purpose is to prevent the tin component in the solder from diffusing into the thermoelectric semiconductor 1 and deteriorating the performance. A conductive material 18 is formed on the surface of the thermoelectric semiconductor 1 for the purpose of ensuring wettability. As the conductive material 18, nickel having a high effect of preventing metal diffusion into the thermoelectric semiconductor 1 is mainly formed.
[0007]
The thermoelectric semiconductor 1 on which the conductive material 18 and the solder 16 are formed is cut with a dicing saw, a wire saw, or the like to form a columnar thermoelectric semiconductor 1 as shown in FIG.
[0008]
A flux 19 is applied on a heat sink 17 on which the metal wiring 4 is formed, and the columnar thermoelectric semiconductor 1 on which the conductive material 18 and the solder 16 are formed as shown in FIG. 13 is p-type and n-type thermoelectric semiconductors as shown in FIG. The semiconductors 1 are arranged alternately.
[0009]
Further, the heat radiating plate 17 on which the other metal wiring 4 is formed is arranged as shown in FIG. 15 via the flux 19, the thermoelectric semiconductor 1 is sandwiched between the heat radiating plates 17, and then formed on the thermoelectric semiconductor 1 by heat treatment. By joining the conductive material 18 and the metal wiring 4 formed on the heat radiating plate 17 with the solder 16 and washing and removing the flux 19, a thermoelectric element as shown in FIG. 16 can be obtained.
As the heat radiating plate 17, a material having good heat conductivity such as silicon or alumina is used. The metal wiring 4 is formed by patterning a film of copper, nickel, gold, or the like formed by a plating method, a sputtering method, a vacuum evaporation method, or the like by etching or the like.
[0010]
[Non-patent document 1]
Kinichi Uemura and Isao Nishida, Thermoelectric Semiconductors and Their Applications, Nikkan Kogyo Shimbun, December 20, 1988, p. 39-41
[0011]
[Problems to be solved by the invention]
The above-described thermoelectric element has the following problems.
[0012]
In the structure of the conventional thermoelectric element, the metal wiring 4 formed on the heat radiating plate 17 and the thermoelectric semiconductor 1 provided with the conductive material 18 on the end face are electrically connected by using the solder 16. Due to expansion or thermal contraction, separation occurs between the conductive material 18 and the thermoelectric semiconductor 1, and the electrical connection between the p-type and n-type thermoelectric semiconductors 1 is broken. Disconnection of the electrical connection is remarkable in a temperature cycle test in which heating and cooling are alternately repeated, and sufficient performance has not been obtained in terms of reliability.
[0013]
Further, although the alumina having a thickness of about 0.5 mm is used as the heat radiating plate 17, the thickness of the heat radiating plate 17 increases the thickness of the entire thermoelectric element, which is a problem when miniaturizing the thermoelectric element. It is a big problem.
[0014]
An object of the present invention is to solve the above problems and provide a small and highly reliable thermoelectric element and a method for manufacturing the same.
[0015]
[Means for Solving the Problems]
In order to achieve the above object, a thermoelectric element and a method of manufacturing the same according to the present invention employ the following configurations and manufacturing methods.
[0016]
The thermoelectric element of the present invention is a thermoelectric element in which a plurality of p-type and n-type thermoelectric semiconductors are alternately arranged via an insulator, and the thermoelectric semiconductors are electrically connected in series by a metal member and a metal wiring. An insulating layer containing heat conductive particles and catalytic metal particles is formed on the metal wiring and the insulator, and the metal layer is formed on the insulating layer.
[0017]
The method for manufacturing a thermoelectric element according to the present invention includes a step of preparing a plurality of p-type and n-type thermoelectric semiconductors arranged via an insulator, and a base for electrically connecting the thermoelectric semiconductors in series. Forming a metal member, and forming a metal wiring on the metal member and on the end surface of the thermoelectric semiconductor where the metal member is not formed; and forming an insulating layer on the surface of the metal wiring and the insulator. And a step of forming a metal layer on the surface of the insulating layer.
[0018]
[Action]
In the thermoelectric element of the present invention, a plurality of p-type and n-type thermoelectric semiconductors are alternately arranged via an insulator, and each thermoelectric semiconductor 1 is electrically connected by a metal member and a metal wiring. The surface is protected by an insulating layer containing heat conductive particles and catalytic metal particles, and the structure is such that a metal layer is formed on the surface of the insulating layer.
[0019]
By forming the insulating layer containing the heat conductive particles and the catalytic metal particles on the surface of the metal wiring and the insulator which electrically connect the plurality of thermoelectric semiconductors, the metal wiring is insulated and protected, and the metal wiring is formed. It is possible to obtain a reinforcing effect of preventing peeling of the wiring.
[0020]
In addition, since the insulating layer contains the heat conductive particles and the catalytic metal particles, when the thermoelectric element is heated or cooled, the loss of heat to be transferred to the object to be cooled and the object to be heated can be reduced, and the catalyst can be reduced. Since it contains metal particles, a metal layer can be formed on the insulating layer by electroless plating with the catalyst metal particles as nuclei, and the object to be cooled or the object to be heated is joined to the metal layer using solder. be able to.
[0021]
Thus, the thermoelectric element can be formed without using the heat sink used in the conventional thermoelectric element, and a small and highly reliable thermoelectric element can be obtained.
[0022]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, a thermoelectric element according to a preferred embodiment of the present invention will be described with reference to the drawings. FIG. 1 shows a cross-sectional view of the thermoelectric element according to the present embodiment. As shown in FIG. 1, a plurality of p-type and n-type thermoelectric semiconductors 1 are alternately arranged via an insulator 2, and each thermoelectric semiconductor 1 is electrically connected by a metal member 3 and a metal wiring 4. The surfaces of the wiring 4 and the insulator 2 are protected by the insulating layer 5 containing the heat conductive particles 10 and the catalytic metal particles 11, and the metal layer 6 is formed on the surface of the insulating layer 5.
[0023]
The metal member 3 is disposed at a portion where the p-type and n-type thermoelectric semiconductors 1 are electrically connected in series, and is formed so as to straddle the thermoelectric semiconductor 1 and the insulator 2 between the thermoelectric semiconductors 1. Thereby, the metal wiring 4 can be formed on the metal member 3 and the thermoelectric semiconductor 1 by electrolytic plating or electroless plating, and at the same time, the p-type and n-type thermoelectric semiconductors 1 can be electrically connected in series.
[0024]
Further, by forming an insulating layer 5 containing heat conductive particles 10 and catalytic metal particles 11 on the surfaces of the metal wires 4 electrically connecting the plurality of thermoelectric semiconductors 1 and the insulator 2, the metal wires 4 are formed. A reinforcing effect of insulating and protecting and preventing peeling of the metal wiring 4 can be obtained.
[0025]
Since the insulating layer 5 contains the heat conductive particles 10 and the catalytic metal particles 11, the loss of heat transferred to the object to be cooled or the object to be heated when the thermoelectric element is heated or cooled can be reduced. Since the catalyst metal particles 11 are contained, the metal layer 6 can be formed on the insulating layer 5 using the catalyst metal particles 11 as a nucleus by an electroless plating method. To the metal layer 6.
[0026]
Thus, the thermoelectric element can be formed without using the heat radiating plate 17 used in the conventional thermoelectric element, and a small and highly reliable thermoelectric element can be obtained.
[0027]
Next, a method for manufacturing a thermoelectric element according to the present embodiment will be described with reference to FIGS. First, as shown in FIG. 2, each of the p-type and n-type thermoelectric semiconductors 1 having a size of 50 mm × 50 mm × 5 mm is formed into a comb-shaped dicing saw so that a groove having a width of 0.6 mm is formed by 1.1 mm. Process at the pitch. Thereafter, an epoxy resin 2280C (trade name) of Three Bond Co., Ltd. was poured into the groove as an insulator 2 while heating to 60 ° C., and the comb-shaped p-type and n-type thermoelectric semiconductors 1 were combined as shown in FIG. The epoxy resin is cured by heating at 130 ° C. for 1 hour. Thereafter, unnecessary portions were removed by grinding to obtain a thermoelectric element block having a structure as shown in FIG.
[0028]
As the thermoelectric semiconductor 1, commonly used bismuth-tellurium-based, antimony-tellurium-based, bismuth-tellurium-antimony-based, bismuth-tellurium-selenium-based and the like can be used, but lead-germanium-based, silicon-germanium-based A thermoelectric semiconductor such as a system can be used.
[0029]
Next, a metal member 3 for connecting the p-type and n-type thermoelectric semiconductors 1 is formed. The method of forming the metal member 3 is as follows. First, a plurality of p-type and n-type thermoelectric semiconductors 1 are alternately arranged via an insulator 2. Then, a metal film is formed by a vacuum evaporation method or a sputtering method, and the metal mask is removed, whereby the metal member 3 is formed only at the opening of the metal mask as shown in FIG. The position where the metal member 3 is formed is a portion where the p-type and n-type thermoelectric semiconductors 1 are electrically connected in series, and is formed so as to straddle the thermoelectric semiconductor 1 and the insulator 2 between the thermoelectric semiconductors 1. I have.
[0030]
When the metal wiring 3 is formed by electroless plating, the metal member 3 functions as a catalyst for starting electroless plating and as a base for performing electroless plating on the insulator 2 between the thermoelectric semiconductors 1. Plays. Therefore, any one of metals belonging to Group VIII of the periodic table is formed as the metal member 3. Further, when the metal wiring 4 is formed by electrolytic plating, it serves only as a base for performing electrolytic plating on the insulator 2 between the thermoelectric semiconductors 1, and thus the type of metal is not particularly limited. In this embodiment, nickel having a high effect of preventing metal diffusion into the thermoelectric semiconductor 1 is formed with a thickness of 0.1 μm.
[0031]
Thereafter, the metal wiring 4 is formed on the metal member 3 and the thermoelectric semiconductor 1 as shown in FIG. 6 by immersing in an electroless nickel plating solution or performing electrolytic nickel plating. In the present embodiment, electroless nickel plating is performed at a solution temperature of 60 ° C. for 10 minutes using an electroless nickel plating solution Top Chemialloy B-1 (trade name) manufactured by Okuno Pharmaceutical Co., Ltd. Metal wiring 4 was formed.
[0032]
Copper was formed to a thickness of 10 μm by electrolytic plating on nickel formed as the metal wiring 4 in order to reduce the resistance of the metal wiring 4, and gold was formed to a thickness of 1 μm to prevent oxidation of the copper surface. For electrolytic copper plating, using electrolytic copper plating solution Microfab Cu200 (trade name) of Japan Electroplating Engineers Co., Ltd., electrolytic copper plating at a liquid temperature of 25 ° C. and a current density of 3 A / dm 2 for 15 minutes, followed by gold plating As for ( 2) , electrolytic gold plating was performed at a liquid temperature of 25 ° C. and a current density of 0.8 A / dm 2 for 2 minutes using an NEC-Cat electrolytic gold plating solution NCF-500 (trade name).
[0033]
Next, as shown in FIG. 7, the insulating layer 5 is applied to the surface of the metal wiring 4 and the insulator 2 by a printing method, and the insulating layer 5 is cured by heating. At this time, the insulating layer 5 hits a power supply portion of the thermoelectric element. The insulating layer 5 is not arranged on the wiring electrode 4. This makes it possible to connect to an external terminal by wire bonding or solder bonding.
[0034]
As the insulating layer 5 formed at this time, as shown in FIG. 8, a base material 12 containing heat conductive particles 10 and catalytic metal particles 11 is used. When the thermoelectric element is heated or cooled by containing the heat conductive particles 10, the reinforcing effect of insulating and protecting the metal wiring 4 and preventing the metal wiring 4 from peeling can be obtained by the base material 12. The loss of heat transmitted to the object to be cooled or the object to be heated can be reduced, and since the catalyst metal particles 11 are contained, the metal layer 6 is electrolessly formed on the insulating layer 5 with the catalyst metal particles 11 as nuclei. It can be formed by a plating method, and an object to be cooled or an object to be heated can be joined to the metal layer 6 using the solder 16.
[0035]
In the present embodiment, 20 parts by weight of epoxy resin 2280C (trade name) of Three Bond Co., Ltd. as base material 12, 75 parts by weight of alumina particles having an average particle diameter of about 10 μm as thermal conductive particles 10, and catalyst metal particles 11 Using a mixture of 5 parts by weight of palladium particles having an average particle diameter of about 3 μm, the base material 12 was cured by heating at 130 ° C. for 1 hour.
[0036]
The type of the base material 12 may be an epoxy-based or acrylic-based adhesive or the like, but is not particularly limited, and the heat conductive particles 10 also have both the thermal conductivity and the insulating property of the insulating layer 5. It is effective to use particles of alumina or aluminum nitride, but the material is not particularly limited. The catalyst metal particles 11 may be of any metal as long as they can be electrolessly plated. Specifically, one or a mixture of one or more kinds of metal particles of group VIII of the periodic table may be used. May be used. Also, the particle diameter and shape of the heat conductive particles 10 and the catalytic metal particles 11 are not particularly limited.
[0037]
Then, as shown in FIG. 9, by immersing in an electroless plating solution, electroless plating starts with the catalyst metal particles 11 in the insulating layer 5 as nuclei, and the metal layer 6 can be formed on the surface of the insulating layer 5. it can. The electroless plating solution used was Top Chemialloy B-1 (trade name) of Okuno Pharmaceutical Co., Ltd., and electroless nickel plating was performed at a solution temperature of 60 ° C. for 10 minutes to form nickel having a thickness of about 1 μm. Using electroless gold plating solution Flash Gold NB manufactured by Okuno Pharmaceutical Co., Ltd., electroless gold plating was performed at a liquid temperature of 90 ° C. for 30 minutes to form gold having a thickness of about 0.1 μm.
[0038]
The thermoelectric element shown in FIG. 1 can be obtained by dividing the dotted line portion of the thermoelectric element shown in FIG. 10 with a dicing saw or a wire saw.
[0039]
The thermoelectric element as shown in FIG. 1 obtained by the above-described process can be configured such that the object to be cooled 15 and the metal layer 6 are joined by using the solder 16 as shown in FIG. The metal layer 6 on the layer 5 and the bonding pattern 14 made of copper, gold, or the like formed on the substrate 13 formed of glass, resin, or the like can be bonded using the solder 16.
[0040]
In the thermoelectric element formed by the above steps, a plurality of p-type and n-type thermoelectric semiconductors 1 are alternately arranged via an insulator 2, and each thermoelectric semiconductor 1 is electrically connected by a metal member 3 and a metal wiring 4. Then, the surfaces of the metal wiring 4 and the insulator 2 are protected by the insulating layer 5 containing the heat conductive particles and the catalytic metal particles, and the metal layer 6 is formed on the surface of the insulating layer 5. .
[0041]
By forming the insulating layer 5 containing the heat conductive particles and the catalytic metal particles on the surfaces of the metal wires 4 electrically connecting the plurality of thermoelectric semiconductors 1 and the insulator 2 in this manner, the metal wires 4 are insulated. Thus, a reinforcing effect of protecting and preventing separation of the metal wiring 4 can be obtained.
[0042]
Further, since the insulating layer 5 contains the heat conductive particles and the catalytic metal particles, it is possible to reduce the loss of heat transferred to the object to be cooled or the object to be heated when the thermoelectric element is heated or cooled, Since the catalyst metal particles are contained, the metal layer 6 can be formed on the insulating layer 5 by the electroless plating method using the catalyst metal as a nucleus. Can be joined.
[0043]
Thus, the thermoelectric element can be formed without using the heat radiating plate 17 used in the conventional thermoelectric element, and a small and highly reliable thermoelectric element can be obtained.
[0044]
【The invention's effect】
As is clear from the above description, the thermoelectric element of the present invention has a plurality of p-type and n-type thermoelectric semiconductors alternately arranged via an insulator, and each thermoelectric semiconductor is electrically connected by a metal member and a metal wiring. The connection and the metal wiring and the surface of the insulator are protected by an insulating layer containing the heat conductive particles and the catalytic metal particles, and the metal layer is formed on the surface of the insulating layer.
[0045]
By forming the insulating layer containing the heat conductive particles and the catalytic metal particles on the surface of the metal wiring and the insulator which electrically connect the plurality of thermoelectric semiconductors, the metal wiring is insulated and protected, and the metal wiring is formed. It is possible to obtain a reinforcing effect of preventing peeling of the wiring.
[0046]
In addition, since the insulating layer contains the heat conductive particles and the catalytic metal particles, when the thermoelectric element is heated or cooled, the loss of heat to be transferred to the object to be cooled and the object to be heated can be reduced, and the catalyst can be reduced. Since it contains metal particles, a metal layer can be formed on the insulating layer by electroless plating using the catalyst metal as a nucleus, and the object to be cooled or the object to be heated is joined to the metal layer 6 using solder. be able to.
[0047]
Thus, the thermoelectric element can be formed without using the heat sink used in the conventional thermoelectric element, and a small and highly reliable thermoelectric element can be obtained.
[Brief description of the drawings]
FIG. 1 is a sectional view showing a thermoelectric element according to an embodiment of the present invention.
FIG. 2 is a cross-sectional view illustrating a method for manufacturing a thermoelectric element according to an embodiment of the present invention.
FIG. 3 is a cross-sectional view illustrating a method for manufacturing a thermoelectric element according to an embodiment of the present invention.
FIG. 4 is a cross-sectional view illustrating a method for manufacturing a thermoelectric element according to an embodiment of the present invention.
FIG. 5 is a cross-sectional view illustrating a method for manufacturing a thermoelectric element according to an embodiment of the present invention.
FIG. 6 is a cross-sectional view illustrating a method for manufacturing a thermoelectric element according to an embodiment of the present invention.
FIG. 7 is a cross-sectional view illustrating a method for manufacturing a thermoelectric element according to an embodiment of the present invention.
FIG. 8 is a cross-sectional view illustrating a method for manufacturing a thermoelectric element according to an embodiment of the present invention.
FIG. 9 is a cross-sectional view illustrating a method for manufacturing a thermoelectric element according to an embodiment of the present invention.
FIG. 10 is a cross-sectional view illustrating a method for manufacturing a thermoelectric element according to an embodiment of the present invention.
FIG. 11 is a cross-sectional view illustrating a structure of a thermoelectric element according to an embodiment of the present invention.
FIG. 12 is a cross-sectional view illustrating a method for manufacturing a thermoelectric element in a conventional example.
FIG. 13 is a perspective view of a thermal semiconductor of a thermoelectric element in a conventional example.
FIG. 14 is a cross-sectional view illustrating a method of manufacturing a thermoelectric element in a conventional example.
FIG. 15 is a cross-sectional view illustrating a method of manufacturing a thermoelectric element in a conventional example.
FIG. 16 is a cross-sectional view illustrating a structure of a thermoelectric element in a conventional example.
[Explanation of symbols]
DESCRIPTION OF SYMBOLS 1 Thermoelectric semiconductor 2 Insulator 3 Metal member 4 Metal wiring 5 Insulating layer 6 Metal layer 10 Heat conductive particles 11 Catalytic metal particles 12 Base material 13 Substrate 14 Joining pattern 15 Cooled object 16 Solder 17 Heat sink 18 Conductive material 19 Flux

Claims (2)

ｐ型とｎ型の複数の熱電半導体を絶縁物を介して交互に配列し、該熱電半導体を金属部材および金属配線によって電気的に直列に接続した熱電素子であって、前記金属配線および前記絶縁物上に熱伝導粒子と触媒金属粒子とを含有した絶縁層が形成されており、該絶縁層上に金属層が形成されている熱電素子。A thermoelectric element in which a plurality of p-type and n-type thermoelectric semiconductors are alternately arranged via an insulator, and the thermoelectric semiconductors are electrically connected in series by a metal member and metal wiring. A thermoelectric element in which an insulating layer containing heat conductive particles and catalytic metal particles is formed on an object, and a metal layer is formed on the insulating layer. 絶縁物を介して配列している複数のｐ型とｎ型の熱電半導体を用意する工程と、該熱電半導体を電気的に直列に接続するための土台となる金属部材を形成する工程と、該金属部材上と該金属部材が形成されていない前記熱電半導体の端部面とに金属配線を形成する工程と、該金属配線および前記絶縁物表面に絶縁層を形成する工程と、該絶縁層表面に金属層を形成する工程とを有する熱電素子の製造方法。A step of preparing a plurality of p-type and n-type thermoelectric semiconductors arranged via an insulator; and forming a metal member serving as a base for electrically connecting the thermoelectric semiconductors in series. Forming a metal wiring on the metal member and the end surface of the thermoelectric semiconductor where the metal member is not formed; forming an insulating layer on the metal wiring and the surface of the insulator; Forming a metal layer on the thermoelectric element.
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EP2131406A1 (en) * 2008-06-02 2009-12-09 Nederlandse Organisatie voor toegepast- natuurwetenschappelijk onderzoek TNO A method for manufacturing a thermoelectric generator, a wearable thermoelectric generator and a garment comprising the same
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JP2011129838A (en) * 2009-12-21 2011-06-30 Fujitsu Ltd Thermoelectric conversion module and method of manufacturing the same
JP2013110157A (en) * 2011-11-17 2013-06-06 Kitagawa Ind Co Ltd Thermoelectric conversion module
JP2014179372A (en) * 2013-03-13 2014-09-25 Kitagawa Kogyo Co Ltd Thermoelectric conversion module
JP2016111326A (en) * 2014-12-09 2016-06-20 パナソニックＩｐマネジメント株式会社 Thermoelectric conversion module and thermoelectric conversion system
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WO2020116803A1 (en) * 2018-12-07 2020-06-11 서울대학교산학협력단 Stretchable and flexible wearable thermoelectric element configured to be coolable and heatable
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CN113285009A (en) * 2021-05-26 2021-08-20 杭州大和热磁电子有限公司 TEC assembled by depositing gold-tin solder and preparation method

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