JP2005217353A - Thermoelectric semiconductor element, thermoelectric transformation module, and method of manufacturing the same - Google Patents
Thermoelectric semiconductor element, thermoelectric transformation module, and method of manufacturing the same Download PDFInfo
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Abstract
Description
本発明は熱電半導体素子、熱電変換モジュールおよびその製造方法に関し、特に、簡単に製造可能であり、かつ任意の形状に成形可能な熱電半導体素子、熱電変換モジュールおよびその製造方法に関するものである。 The present invention relates to a thermoelectric semiconductor element, a thermoelectric conversion module, and a manufacturing method thereof, and more particularly to a thermoelectric semiconductor element, a thermoelectric conversion module, and a manufacturing method thereof that can be easily manufactured and can be formed into an arbitrary shape.
従来、ペルチェ効果素子やゼーベック効果素子などの熱電半導体素子は、１素子ペア当たりの駆動電圧あるいは発生電圧が小さいので、多数の素子ペアを直列接続する必要があった。そのために、合金形成されたｐ型とｎ型の熱電半導体をΠ（パイ）形に立て、上部面同士、下部面同士をそれぞれ電極により交互に接合して全ての素子が直列に接続し、更に上面および下面を絶縁体の板によって挟む構造が主であった。例えば、下記の文献には、従来の熱電半導体素子を用いた熱電変換モジュールが開示されている。
上記した従来の熱電半導体素子および同素子を用いた熱電変換モジュールにおいては、ｎ型およびｐ型の熱電半導体素子を交互に並べて配置し、隣接するそれぞれの素子の端子同士を接続するために製造に手間がかかり、価格が高くなってしまうという問題点があった。また、素子の形状が限定されるために、任意の形状に成形することが困難であり、フレキシブル性を持たせることも困難であるという問題点もあった。 In the conventional thermoelectric semiconductor element and the thermoelectric conversion module using the element, the n-type and p-type thermoelectric semiconductor elements are alternately arranged and are manufactured to connect the terminals of adjacent elements. There was a problem that it took time and the price was high. In addition, since the shape of the element is limited, it is difficult to form the element into an arbitrary shape, and it is difficult to provide flexibility.
本発明は、上記した課題を解決することを目的とし、このために、本発明の装置は、熱電半導体の微粉末を導電性を付与したゴムや樹脂などの有機物あるいはガラスへ添加し、混練してペースト状にした半導体を用いることを主要な特徴とする。また、基板の孔あるいは窪みにペースト状の熱電半導体素子を充填するか、あるいは基板にペースト状の熱電半導体素子を塗布することによって製造された熱電変換モジュールにも特徴がある。更に、熱電半導体素子が形成された基板が複数個積層されている点にも特徴がある。 The present invention aims to solve the above-described problems, and for this purpose, the apparatus of the present invention adds a thermoelectric semiconductor fine powder to an organic substance such as rubber or resin or glass imparted with conductivity, and kneads. The main feature is to use a paste-like semiconductor. Further, the thermoelectric conversion module manufactured by filling a hole or depression in the substrate with a paste-like thermoelectric semiconductor element or applying a paste-like thermoelectric semiconductor element to the substrate is also characterized. Furthermore, there is a feature in that a plurality of substrates on which thermoelectric semiconductor elements are formed are stacked.
本発明の装置は上記のような特徴によって、熱電半導体素子を印刷技術等によって簡単に大量生産することができ、積層化も容易であるという効果がある。また、熱電半導体素子の大きさや形状を自由に設計でき、高温側と低温側の距離を離すことが可能となる。また、基板や混合する樹脂として熱伝導率の小さいものを採用可能であり、高温側から低温側への熱伝導量を減少させることができるという効果がある。更に、基板にフレキシブル性を持たせることにより熱電変換モジュールを曲面形状に成形するか、あるいは成形後に変形させることができるという効果がある。 Due to the above-described features, the apparatus of the present invention has an effect that thermoelectric semiconductor elements can be easily mass-produced by a printing technique or the like and can be easily laminated. Further, the size and shape of the thermoelectric semiconductor element can be freely designed, and the distance between the high temperature side and the low temperature side can be increased. In addition, it is possible to employ a substrate or a resin having a low thermal conductivity as a resin to be mixed, and there is an effect that the amount of heat conduction from the high temperature side to the low temperature side can be reduced. Furthermore, by giving the substrate flexibility, there is an effect that the thermoelectric conversion module can be formed into a curved surface shape or deformed after the forming.
以下、図面を参照して実施例について説明する。 Embodiments will be described below with reference to the drawings.
図１は、本発明の熱電半導体素子を使用して製造された実施例１の熱電変換モジュールの構成を示す断面図である。基板１０に設けられた複数の孔に交互にｐ型熱電半導体素子１１およびｎ型熱電半導体素子１２が形成され、隣接するそれぞれの素子１１、１２の端部同士が電極（接続回路）１３によって直列に接続されている。更に、モジュールの表面全体を絶縁層１４が覆っている。
FIG. 1 is a cross-sectional view showing a configuration of a thermoelectric conversion module of Example 1 manufactured using the thermoelectric semiconductor element of the present invention. A p-type thermoelectric semiconductor element 11 and an n-type thermoelectric semiconductor element 12 are alternately formed in a plurality of holes provided in the
図２は、本発明の実施例１の熱電変換モジュールの製造工程（その１）を示す断面図である。図２（ａ）においては、まず基板１０に熱電半導体素子を形成するための孔１５を開ける。基板としては、例えば樹脂などのプラスチック製絶縁材料を素材とした板を採用可能であり、なるべく熱伝導率が小さいものが望ましい。孔開け方法としては、ドリル、プレス、プラスチック成形金型、レーザー、アルカリエッチングなどを採用可能である。
FIG. 2 is a cross-sectional view illustrating a manufacturing process (No. 1) of the thermoelectric conversion module according to the first embodiment of the present invention. In FIG. 2A, first, a hole 15 for forming a thermoelectric semiconductor element is formed in the
図２（ｂ）においては、ｐ型熱電半導体素子１１を形成する孔のみを残し、ｎ型熱電半導体素子１２を形成する孔を感光性ドライフィルムラミネート法、常温接着テープによってフィルム１６によりマスクする。なお、このようなフィルムおよびマスク方法は公知である。
図２（ｃ）においては、ｐ型熱電半導体素子１１を形成する孔１５にペースト状のｐ型熱電半導体素子１１を充填する。
In FIG. 2B, only the hole for forming the p-type thermoelectric semiconductor element 11 is left, and the hole for forming the n-type thermoelectric semiconductor element 12 is masked with the film 16 by a photosensitive dry film laminating method and room temperature adhesive tape. Such film and mask methods are well known.
In FIG. 2 (c), the paste-type p-type thermoelectric semiconductor element 11 is filled in the hole 15 for forming the p-type thermoelectric semiconductor element 11.
本発明の熱電半導体素子は、以下の材料を混合し、混練してペースト状にする。（１）ｎ型あるいはｐ型熱電半導体微粉末、（２）導電性微粉末、（３）熱硬化性樹脂、ガラスあるいはゴム（４）分散剤。
ｎ型あるいはｐ型熱電半導体としては、例えばビスマステルル（Bi2Te3）などの熱電半導体材料にｎ型あるいはｐ型とするための不純物を添加したものなど、公知の任意の熱電半導体材料を使用可能である。
In the thermoelectric semiconductor element of the present invention, the following materials are mixed and kneaded into a paste. (1) n-type or p-type thermoelectric semiconductor fine powder, (2) conductive fine powder, (3) thermosetting resin, glass or rubber (4) dispersant.
As the n-type or p-type thermoelectric semiconductor, for example, any known thermoelectric semiconductor material, such as a thermoelectric semiconductor material such as bismuth tellurium (Bi 2 Te 3 ) added with an impurity for making it n-type or p-type is used. Is possible.
導電性微粉末としては、例えば金属粉末、カーボン粉末等を使用可能である。熱硬化性樹脂としては、溶剤を含む熱硬化性樹脂、あるいは溶剤を含まない熱硬化性樹脂を使用する。例を挙げれば、エポキシ樹脂、フェノール樹脂、シリコーン樹脂等を使用可能である。また、樹脂の代わりにガラスやゴム、エラストマーでもよい。ガラスの場合には、ガラス＋溶剤（α-テルピネオール等）でペースト状になる。なお、素材の微粉末として非常に細かいナノ粒子を使用してもよい。分散剤としては、例えばアルキルアセトアセテートアルミニウムジイソプロピレートを使用可能である。 As the conductive fine powder, for example, metal powder, carbon powder or the like can be used. As the thermosetting resin, a thermosetting resin containing a solvent or a thermosetting resin containing no solvent is used. For example, an epoxy resin, a phenol resin, a silicone resin, or the like can be used. Further, glass, rubber, or elastomer may be used instead of resin. In the case of glass, it becomes a paste with glass + solvent (such as α-terpineol). In addition, you may use a very fine nanoparticle as a fine powder of a raw material. As the dispersant, for example, alkyl acetoacetate aluminum diisopropylate can be used.
図２（ｄ）においては、マスク用のフィルム１６を除去し、熱風などにより加熱してペースト状の半導体１１を硬化させる。図２（ｅ）においては、基板１０の面と半導体面を平滑にするためロール型研磨剤あるいは平面研磨、サンドブラストにより平滑研磨する。
In FIG. 2D, the mask film 16 is removed, and the paste-like semiconductor 11 is cured by heating with hot air or the like. In FIG. 2 (e), the surface of the
図３は、本発明の実施例１の熱電変換モジュールの製造工程（その２）を示す断面図である。図３（ｆ）においては、ｎ型熱電半導体素子１２について図２（ｃ）、（ｄ）の処理を繰り返し、ｎ型熱電半導体素子１２を形成する。図３（ｇ）においては、基板１０の面と半導体面を平滑にするためロール型研磨剤により平滑研磨する。
FIG. 3 is a cross-sectional view illustrating a manufacturing process (No. 2) of the thermoelectric conversion module according to the first embodiment of the present invention. In FIG. 3F, the n-type thermoelectric semiconductor element 12 is formed by repeating the processes of FIGS. 2C and 2D for the n-type thermoelectric semiconductor element 12. In FIG. 3G, the surface of the
図３（ｈ）においては、メッキ＋エッチング法、導電ペースト印刷法などの公知の回路形成方法によって素子の端部同士を直列に接続する電極１３を形成する。図３（ｉ）においては、外部との接続部分の電極を残し、その他の部分の表面を絶縁層１４によって覆う。以上のような工程を経て図１に示すよう１層の熱電変換モジュールが完成する。 In FIG. 3H, the electrodes 13 for connecting the end portions of the elements in series are formed by a known circuit forming method such as a plating + etching method or a conductive paste printing method. In FIG. 3 (i), the electrode of the connection portion with the outside is left, and the surface of the other portion is covered with the insulating layer 14. Through the steps described above, a one-layer thermoelectric conversion module is completed as shown in FIG.
なお、ペースト状の半導体の埋め込み方法としては、上記した方法以外にスクリーンマスク、メタルマスクを用い、スキージにより埋め込む印刷法、または、ロールコーター、スプレーコーター、マルチヘッドディスペンサー（吐出装置）により埋め込む方法、超音波によって孔内のエアーを除きディップするディップ（浸漬）法、凹版方式などを採用してもよい。 In addition, as a method for embedding a paste-like semiconductor, in addition to the above-described method, a screen mask or a metal mask is used, a printing method for embedding with a squeegee, or a method for embedding with a roll coater, spray coater, multi-head dispenser (discharge device), You may employ | adopt the dip (immersion) method, the intaglio method, etc. which dip except the air in a hole with an ultrasonic wave.
また、上記した工程の変形例として、まずｐ型熱電半導体素子１１用のみの孔を開け、ｐ型ペーストを充填し、乾燥、平滑研磨した後、ｎ型熱電半導体素子１２用のみの孔を開け、ｎ型ペーストを充填し、乾燥、平滑研磨する方法も可能である。 As a modification of the above-described process, first, a hole only for the p-type thermoelectric semiconductor element 11 is formed, filled with p-type paste, dried and smooth polished, and then a hole only for the n-type thermoelectric semiconductor element 12 is formed. Also, a method of filling n-type paste, drying and smooth polishing is possible.
以上のような工程により、常温〜３５０度程度の熱処理によって素子を形成可能である。また、ナノ粒子を使用することにより、更に低温で素子を形成可能となる。 Through the steps as described above, the element can be formed by a heat treatment at a room temperature to about 350 degrees. Moreover, it becomes possible to form an element at a lower temperature by using nanoparticles.
図５は、本発明の熱電半導体素子を使用して製造された実施例１の熱電変換モジュールの構成を示す平面図である。図５（ａ）は一方の面の平面図であり、（ｂ）は他方の面の平面図である。電極１３は実際にはｐ型熱電半導体素子１１およびｎ型熱電半導体素子１２の頭部全体を覆っている。全ての半導体素子１１、１２は直列に接続されており、図５（ａ）の左上部および右下部にある外部接続用電極によって外部と接続される。 FIG. 5 is a plan view showing the configuration of the thermoelectric conversion module of Example 1 manufactured using the thermoelectric semiconductor element of the present invention. FIG. 5A is a plan view of one surface, and FIG. 5B is a plan view of the other surface. The electrode 13 actually covers the entire heads of the p-type thermoelectric semiconductor element 11 and the n-type thermoelectric semiconductor element 12. All the semiconductor elements 11 and 12 are connected in series, and are connected to the outside by the external connection electrodes on the upper left and lower right in FIG.
図６は、ｐ型熱電半導体素子１１およびｎ型熱電半導体素子１２の配置例を示す説明図である。図６（ａ）は図５に示した実施例１の配置である。この場合にはｐ型熱電半導体素子１１およびｎ型熱電半導体素子１２が交互に配置されるので、充填時のマスクの形成等において細かいパターンが必要である。 FIG. 6 is an explanatory view showing an arrangement example of the p-type thermoelectric semiconductor element 11 and the n-type thermoelectric semiconductor element 12. FIG. 6A shows the arrangement of the first embodiment shown in FIG. In this case, since the p-type thermoelectric semiconductor elements 11 and the n-type thermoelectric semiconductor elements 12 are alternately arranged, a fine pattern is required for forming a mask during filling.
図６（ｂ）は（ａ）のパターンを１行おきに１素子分ずらしたもので、電極の接続パターンを長くすることなく、同じ種類の素子を１列に配置することができる。図６（ｃ）は同じ種類の素子を隣接する複数列に配置したものである。このような配置にすれば充填時のマスクの形成等は容易になるが、全ての素子を交互に直列に接続するための電極の接続パターンが複雑となる。なお、最密充填配置等も可能である。また、孔の数、密度、大きさ、深さ、断面形状は任意である。 In FIG. 6B, the pattern of FIG. 6A is shifted by one element every other row, and the same type of elements can be arranged in one column without lengthening the electrode connection pattern. FIG. 6C shows the same type of elements arranged in a plurality of adjacent rows. With such an arrangement, it becomes easy to form a mask at the time of filling, but the connection pattern of electrodes for alternately connecting all elements in series becomes complicated. A close-packed arrangement or the like is also possible. The number, density, size, depth, and cross-sectional shape of the holes are arbitrary.
図４は、本発明の熱電半導体素子を使用して製造された実施例２の熱電変換モジュールの構成を示す断面図である。実施例２の熱電変換モジュールは、実施例１の熱電変換モジュールを複数枚積層したものである。各層間はスルーホール１８によって接続される。このような構造は積層印刷配線板の製造技術を使用して製造可能である。 FIG. 4 is a cross-sectional view showing the configuration of the thermoelectric conversion module of Example 2 manufactured using the thermoelectric semiconductor element of the present invention. The thermoelectric conversion module of Example 2 is obtained by stacking a plurality of thermoelectric conversion modules of Example 1. Each layer is connected by a through hole 18. Such a structure can be manufactured using a technique for manufacturing a laminated printed wiring board.
実施例２の熱電変換モジュールは、１素子当たりの熱移動方向の長さをあまり長くすることなく、全体としては高温側と低温側の距離を長くすることができるので、駆動電流を増やせると共に直列接続する素子数も増やすことができる。 The thermoelectric conversion module according to the second embodiment can increase the driving current as well as the distance between the high temperature side and the low temperature side as a whole without increasing the length of the heat transfer direction per element so much. The number of connected elements can also be increased.
図７は、本発明の熱電半導体素子を使用して製造された実施例３の熱電変換モジュールの部品構成を示す平面図である。第３実施例は堅いあるいはフレキシブルな基板３０の表面に熱電半導体素子を形成する例である。図７（ａ）、（ｂ）は、ｐ型熱電半導体素子３１およびｎ型熱電半導体素子３２を接続する電極３３が基板３０の中央部に配置された部品を示す平面図および断面図である。この場合には中央部（３３）と両端部（３４、３５）の間に温度差が発生する。
FIG. 7 is a plan view showing the component structure of the thermoelectric conversion module of Example 3 manufactured using the thermoelectric semiconductor element of the present invention. The third embodiment is an example in which a thermoelectric semiconductor element is formed on the surface of a rigid or
図７（ｃ）、（ｄ）は、ｐ型熱電半導体素子３１およびｎ型熱電半導体素子３２を接続する電極３３が基板３０の端部に配置された部品を示す平面図および断面図である。この場合には図７（ｃ）の上端（３３）と下端（３４、３５）の間に温度差が発生する。
FIGS. 7C and 7D are a plan view and a cross-sectional view showing a component in which an electrode 33 that connects the p-type thermoelectric semiconductor element 31 and the n-type thermoelectric semiconductor element 32 is arranged at the end of the
ｐ型熱電半導体素子３１およびｎ型熱電半導体素子３２は実施例１と同じペースト状の熱電半導体素子を公知の印刷法等によって所望の位置に塗布し、加熱硬化させる。電極３３、３４、３５も実施例１と同様の方法により形成する。
For the p-type thermoelectric semiconductor element 31 and the n-type thermoelectric semiconductor element 32, the same paste-like thermoelectric semiconductor element as in Example 1 is applied to a desired position by a known printing method or the like, and is cured by heating. The
図８は、図７（ｃ）に示した熱電変換モジュール部品を複数枚積層した実施例３の熱電変換モジュールの構成を示す斜視図および断面図である。図７（ｃ）に示した熱電変換モジュール部品４０を積層し、スルーホール４３によってそれぞれの層４０の電極同士を１つおきに交互に接続する。できたモジュールは例えば上面４１が発熱面、下面４２が吸熱面となる。
FIG. 8 is a perspective view and a cross-sectional view showing the configuration of the thermoelectric conversion module of Example 3 in which a plurality of thermoelectric conversion module components shown in FIG. The thermoelectric
図９は、本発明の熱電半導体素子を使用して製造された実施例４の熱電変換モジュールの構成を示す平面図である。実施例３は１基板当たり１ペアの熱電半導体素子が形成されていたが、実施例４は、１枚の基板５０上に複数ペアの熱電半導体素子が形成された例である。図９においては、横方向に４ペア、縦（熱移動）方向に４層（ペア）の熱電半導体素子が形成されており、接続回路５１によって縦方向の接続が形成されている。なお、横方向および縦（熱移動）方向のペア数は１以上の任意である。なお、図８（ｂ）の断面図に示すように、スルーホールによる層間接続を容易にするために、１層おきにｐ型熱電半導体素子３１およびｎ型熱電半導体素子３２の配置を逆にする。
FIG. 9 is a plan view showing the configuration of the thermoelectric conversion module of Example 4 manufactured using the thermoelectric semiconductor element of the present invention. In Example 3, one pair of thermoelectric semiconductor elements is formed per substrate, but Example 4 is an example in which a plurality of pairs of thermoelectric semiconductor elements are formed on one
実施例４の変形例としては、ポリエステル、ポリイミドなどの長いテープ状のフレキシブル基板上の長手方向に複数のｐ型熱電半導体素子３１およびｎ型熱電半導体素子３２を交互に塗布し、電極で直列接続することによって、テープ状の熱電変換モジュールを作成する。そして、素子や電極同士が接触／導通しないようにフィルムを挿入するなどして、絶縁状態で１ペア毎にあるいは複数ペア毎に折り畳むことにより熱電変換モジュールを作成する。このようにすれば、全ての素子は直列に接続されているので、折り畳むだけでモジュールが完成し、層間の接続を形成する工程が不要となる。 As a modification of the fourth embodiment, a plurality of p-type thermoelectric semiconductor elements 31 and n-type thermoelectric semiconductor elements 32 are alternately applied in the longitudinal direction on a long tape-shaped flexible substrate such as polyester and polyimide, and are connected in series with electrodes. By doing so, a tape-shaped thermoelectric conversion module is created. And a thermoelectric conversion module is created by inserting a film so that elements and electrodes do not come into contact / conducting, or by folding each element or every pair in an insulated state. In this way, since all the elements are connected in series, the module is completed simply by folding, and the step of forming the connection between layers is not necessary.
以上実施例を説明したが、本発明には以下のような変形例も考えられる。実施例においては孔にペースト状の半導体を充填する例を開示したが、底に予め電極を形成した窪みにペースト状の半導体を充填するか塗布するようにすることも可能である。 Although the embodiments have been described above, the following modifications may be considered in the present invention. In the embodiment, an example in which the hole is filled with the paste-like semiconductor has been disclosed. However, it is also possible to fill or apply the paste-like semiconductor to the recess in which the electrode is previously formed on the bottom.
実施例においては熱電半導体素子を使用する例を開示したが、本発明のモジュール製造方法は、粉末状にすることが可能な任意の機能性素子を使用したモジュールの製造に適用可能である。 Although the example using a thermoelectric semiconductor element was disclosed in the Example, the module manufacturing method of this invention is applicable to manufacture of the module using the arbitrary functional elements which can be made into a powder form.
１０ 基板
１１ ｐ型熱電半導体素子
１２ ｎ型熱電半導体素子
１３ 電極（接続回路）
１４ 絶縁層
１５ 孔
10 substrate 11 p-type thermoelectric semiconductor element 12 n-type thermoelectric semiconductor element 13 electrode (connection circuit)
14 Insulating layer 15 hole
Claims (6)
前記熱電半導体の微粉末と導電性微粉末とを有機物あるいはガラスへ添加してペースト状にしたことを特徴とする請求項１に記載の熱電半導体素子。 The conductive fine powder is a fine powder of metal or carbon,
The thermoelectric semiconductor element according to claim 1, wherein the thermoelectric semiconductor fine powder and the conductive fine powder are added to an organic substance or glass to form a paste.
ペースト状の熱電半導体素子を基板の所望の箇所に塗布あるいは充填する工程、
熱電半導体素子を硬化させる工程、
を含むことを特徴とする熱電変換モジュールの製造方法。
Manufacturing a paste-like thermoelectric semiconductor element in which a fine powder of a thermoelectric semiconductor and a conductive fine powder are mixed,
A step of applying or filling a paste-like thermoelectric semiconductor element into a desired portion of the substrate;
Curing the thermoelectric semiconductor element;
The manufacturing method of the thermoelectric conversion module characterized by including.
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