JP2003069091A - Ceramic substrate for thermoelectric exchange module - Google Patents
Ceramic substrate for thermoelectric exchange moduleInfo
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- JP2003069091A JP2003069091A JP2001257611A JP2001257611A JP2003069091A JP 2003069091 A JP2003069091 A JP 2003069091A JP 2001257611 A JP2001257611 A JP 2001257611A JP 2001257611 A JP2001257611 A JP 2001257611A JP 2003069091 A JP2003069091 A JP 2003069091A
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- Prior art keywords
- ceramic substrate
- layer
- thermoelectric
- exchange module
- electrode
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- Cooling Or The Like Of Semiconductors Or Solid State Devices (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、光通信分野等に使
用される半導体レーザ（ＬＤ），フォトダイオード（Ｐ
Ｄ）等の光半導体素子を作動時に冷却するための熱電交
換モジュール用セラミック基板に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a semiconductor laser (LD) and a photodiode (P) used in the field of optical communication and the like.
The present invention relates to a ceramic substrate for a thermoelectric exchange module for cooling an optical semiconductor element such as D) during operation.
【０００２】[0002]
【従来の技術】従来の光通信分野等に使用されるＬＤ，
ＰＤ等の光半導体素子を作動時に冷却するための熱電交
換モジュールは、光半導体素子の作動時に発する熱を外
部へ伝えることにより、光半導体素子を常に一定の温度
に保持する熱電冷却装置として機能する。この熱電交換
モジュール、即ち熱電冷却装置は、セラミック基板の主
面においてｐ型とｎ型の熱電素子を電気的に直列または
並列に接続して一体構造とした状態で、ペルチェ効果を
利用して高温端の電極および低温端の電極に印加した電
圧に依存して温度差を生じさせることにより一端を冷却
するものである。2. Description of the Related Art LDs used in conventional optical communication fields,
A thermoelectric exchange module for cooling an opto-semiconductor element such as a PD operates as a thermoelectric cooling device that always keeps the opto-semiconductor element at a constant temperature by transmitting heat generated when the opto-semiconductor element is actuated to the outside. . This thermoelectric exchange module, that is, a thermoelectric cooling device, utilizes a Peltier effect to increase the temperature at a high temperature in a state in which p-type and n-type thermoelectric elements are electrically connected in series or in parallel on the main surface of a ceramic substrate. One end is cooled by producing a temperature difference depending on the voltage applied to the end electrode and the low temperature end electrode.
【０００３】そして、従来の熱電交換モジュール用セラ
ミック基板は、図３に電極周辺部の断面図を示すよう
に、アルミナ（Ａｌ2Ｏ3）セラミックスや窒化アルミニ
ウム（ＡｌＮ）セラミックス等のセラミック基板１０１
の一方の主面に、複数の電極となる銅（Ｃｕ）層１０２
ｂが被着されている。このＣｕ層１０２ｂは、セラミッ
ク基板１０１の一方の主面全面に無電解メッキによるＣ
ｕ層を被着させた後、Ｃｕ層１０２ｂを形成しない部位
にメッキレジストを施し、さらに電解メッキによるＣｕ
層をメッキレジストの高さよりも低い位置まで被着さ
せ、その後メッキレジストを剥離するとともにメッキレ
ジスト直下の無電解メッキによるＣｕ層をエッチング等
により除去することにより、それぞれ独立した（電気的
に絶縁された）複数の電極となる。A conventional ceramic substrate for a thermoelectric exchange module has a ceramic substrate 101 made of alumina (Al 2 O 3 ) ceramics, aluminum nitride (AlN) ceramics or the like, as shown in the sectional view of the electrode peripheral portion in FIG.
A copper (Cu) layer 102 serving as a plurality of electrodes on one main surface of
b is applied. The Cu layer 102b is formed by electroless plating of C on the entire one main surface of the ceramic substrate 101.
After depositing the u layer, a plating resist is applied to a portion where the Cu layer 102b is not formed, and then Cu is formed by electrolytic plating.
The layers are deposited to a position lower than the height of the plating resist, and then the plating resist is peeled off and the Cu layer formed by electroless plating directly below the plating resist is removed by etching or the like. It has multiple electrodes.
【０００４】さらに、Ｃｕ層１０２ｂの上面の平坦部に
ニッケル（Ｎｉ）メッキ層と金（Ａｕ）メッキ層を順に
被着させ、錫（Ｓｎ）−銀（Ａｇ）系，Ｓｎ−アンチモ
ン（Ｓｂ）系，Ｓｎ−ビスマス（Ｂｉ）系，Ｓｎ−鉛
（Ｐｂ）系等の半田を介して、ｐ型，ｎ型の熱電素子１
０３を固着することにより、製品としての熱電交換モジ
ュールが作製される。Further, a nickel (Ni) plating layer and a gold (Au) plating layer are sequentially deposited on the flat portion of the upper surface of the Cu layer 102b, and tin (Sn) -silver (Ag) system and Sn-antimony (Sb) are deposited. System, Sn-bismuth (Bi) system, Sn-lead (Pb) system or the like via a p-type or n-type thermoelectric element 1
By fixing 03, a thermoelectric exchange module as a product is manufactured.
【０００５】上記の熱電交換モジュールにより、光半導
体素子等の発熱体が作動時に発する熱は、熱電素子１０
３からＣｕ層１０２ｂ、セラミック基板１０１を介して
外部へ効率良く伝えられる。With the thermoelectric exchange module described above, the heat generated by a heating element such as an optical semiconductor element during operation is generated by the thermoelectric element 10
3 is efficiently transmitted to the outside through the Cu layer 102b and the ceramic substrate 101.
【０００６】[0006]
【発明が解決しようとする課題】しかしながら、発熱体
の作動時における熱量が非常に大きいため、より大きな
電流を流してペルチェ効果をさらに発揮させなければな
らない場合、従来の技術では、２つの大きな問題点があ
る。However, when the amount of heat during operation of the heating element is so large that a larger current must be passed to further exert the Peltier effect, the conventional technique has two major problems. There is a point.
【０００７】まず第１に、セラミック基板１０１がより
高温となりセラミック基板１０１とＣｕ層１０２ｂとの
熱膨張差による熱応力がより大きくなり、Ｃｕ層１０２
ｂの外周端のセラミック基板１０１と接合されている部
位を起点として、それらの間で剥がれが発生することが
ある。そのため、発熱体が作動時に発する熱が、Ｃｕ層
１０２ｂからセラミック基板１０１に効率良く伝わら
ず、その結果、発熱体が作動時に発する熱が外部に効率
良く伝達し難くなり発熱体の作動性が劣化するという問
題があった。First, the temperature of the ceramic substrate 101 becomes higher, and the thermal stress due to the difference in thermal expansion between the ceramic substrate 101 and the Cu layer 102b becomes larger.
Starting from a portion of the outer peripheral end of b that is joined to the ceramic substrate 101, peeling may occur between them. Therefore, the heat generated when the heating element operates is not efficiently transferred from the Cu layer 102b to the ceramic substrate 101, and as a result, the heat generated when the heating element operates is difficult to efficiently transmit to the outside, and the operability of the heating element deteriorates. There was a problem of doing.
【０００８】そこで、図４（ａ）に電極部の拡大断面図
を示すように、セラミック基板１０１の一方の主面に、
モリブデン（Ｍｏ），マンガン（Ｍｎ），タングステン
（Ｗ）等の粉末に有機溶剤，溶媒を添加混合して得た金
属ペーストをスクリーン印刷法により印刷塗布し焼結す
ることによりメタライズ層１０２ａを形成し、このメタ
ライズ層１０２ａをセラミック基板１０１とＣｕ層１０
２ｂとの強固な接合媒体として機能させる構成もある。
なお、この場合、メタライズ層１０２ａとＣｕ層１０２
ｂとで電極１０２が構成される。Therefore, as shown in the enlarged cross-sectional view of the electrode portion in FIG. 4A, one main surface of the ceramic substrate 101 is
A metallized layer 102a is formed by printing and applying a metal paste obtained by adding and mixing an organic solvent and a solvent to powders of molybdenum (Mo), manganese (Mn), tungsten (W), etc. by screen printing and sintering. The metallized layer 102a is used as the ceramic substrate 101 and the Cu layer 10.
There is also a configuration in which it functions as a strong joining medium with 2b.
In this case, the metallized layer 102a and the Cu layer 102
The electrode 102 is constituted by b.
【０００９】しかしながら、図４（ｂ）に図４（ａ）の
要部拡大断面図を示すように、メタライズ層１０２ａの
外周端の形状は、その厚さ，印刷塗布条件，焼結等の製
造条件によって、セラミック基板１０１と電極１０２と
の熱膨張差による熱応力を、メタライズ層１０２ａの外
周端が十分に吸収し緩和させることが困難な形状とな
る。即ち、従来、メタライズ層１０２ａの外周端は外側
に向かって凸の曲面、またはセラミック基板１０１に対
してほぼ垂直な面となっており、図３の場合よりもセラ
ミック基板１０１と電極１０２との接合強度は向上する
が、熱応力が発生した際に吸収し緩和させ難い。つま
り、メタライズ層１０２ａの外周端の接合部がセラミッ
ク基板１０１に対してほぼ垂直になっているため、セラ
ミック基板１０１と電極１０２との間で発生した面方向
の熱応力によって、メタライズ層１０２ａの外周端が剥
離し易くなっていると考えられる。However, as shown in FIG. 4 (b), which is an enlarged cross-sectional view of the main part of FIG. 4 (a), the outer peripheral edge of the metallized layer 102a is shaped such that its thickness, print coating conditions, sintering, etc. Depending on the conditions, the thermal stress due to the difference in thermal expansion between the ceramic substrate 101 and the electrode 102 is sufficiently absorbed by the outer peripheral end of the metallized layer 102a and is difficult to relax. That is, conventionally, the outer peripheral edge of the metallized layer 102a is a curved surface that is convex outward, or a surface that is substantially perpendicular to the ceramic substrate 101, and the ceramic substrate 101 and the electrode 102 are bonded to each other more than in the case of FIG. Strength is improved, but it is difficult to absorb and relax when thermal stress occurs. That is, since the joint portion at the outer peripheral end of the metallized layer 102a is substantially perpendicular to the ceramic substrate 101, the thermal stress in the surface direction generated between the ceramic substrate 101 and the electrode 102 causes the outer periphery of the metallized layer 102a. It is considered that the edges are easily peeled off.
【００１０】第２に、セラミック基板１０１がより高温
になるに伴い、電極１０２の一部を構成するＣｕ層１０
２ｂもより高温となる。そのため、Ｃｕ層１０２ｂと熱
電素子１０３との熱膨張差による熱応力がより大きく成
り、Ｃｕ層１０２ｂと熱電素子１０３とが接合されてい
る部位を起点として、それらの間で剥がれが発生するこ
とがある。そのため、発熱体が作動時に発する熱が、熱
電素子１０３からＣｕ層１０２ｂに効率良く伝わらず、
その結果、発熱体が作動時に発する熱が外部に効率良く
伝達し難くなり発熱体の作動性が劣化するという問題が
あった。Second, as the temperature of the ceramic substrate 101 becomes higher, the Cu layer 10 forming a part of the electrode 102 is formed.
2b also becomes hotter. Therefore, the thermal stress due to the difference in thermal expansion between the Cu layer 102b and the thermoelectric element 103 becomes larger, and peeling may occur between the Cu layer 102b and the thermoelectric element 103, starting from the joint. is there. Therefore, the heat generated when the heating element operates does not efficiently transfer from the thermoelectric element 103 to the Cu layer 102b,
As a result, there is a problem that it is difficult to efficiently transfer the heat generated by the heating element to the outside, and the operability of the heating element deteriorates.
【００１１】上記のように、セラミック基板１０１と電
極１０２との間で発生した熱応力、および電極１０２と
熱電素子１０３との間で発生した熱応力により、それぞ
れセラミック基板１０１とメタライズ層１０２ａとの間
の剥がれや、Ｃｕ層１０２ｂと熱電素子１０３との間の
剥がれが発生し、発熱体が作動時に発する熱を外部に効
率良く伝達し難くなり、発熱体の作動性が劣化するとい
う問題があった。As described above, due to the thermal stress generated between the ceramic substrate 101 and the electrode 102 and the thermal stress generated between the electrode 102 and the thermoelectric element 103, the ceramic substrate 101 and the metallized layer 102a are respectively formed. There is a problem in that peeling occurs between the Cu layer 102b and the thermoelectric element 103, and it becomes difficult to efficiently transfer the heat generated by the heating element to the outside, and the operability of the heating element deteriorates. It was
【００１２】従って、本発明は上記問題点に鑑み完成さ
れたものであり、その目的は、セラミック基板と電極と
の熱膨張差により発生する熱応力、および電極と熱電素
子との熱膨張差により発生する熱応力を十分に吸収し緩
和させることにより、光半導体素子等の発熱体から発す
る熱を外部に効率良く伝達させ得る熱電交換モジュール
用セラミック基板を提供することにある。Therefore, the present invention has been completed in view of the above problems, and an object of the present invention is to provide a thermal stress generated by a difference in thermal expansion between a ceramic substrate and an electrode and a thermal expansion difference between an electrode and a thermoelectric element. It is an object of the present invention to provide a ceramic substrate for a thermoelectric exchange module which can efficiently transfer heat generated from a heating element such as an optical semiconductor element to the outside by sufficiently absorbing and relaxing the generated thermal stress.
【００１３】[0013]
【課題を解決するための手段】本発明の熱電交換モジュ
ール用セラミック基板は、セラミック基板の一方の主面
に、上面に熱電素子が載置固定される電極がそれぞれ独
立して複数形成された熱電交換モジュール用セラミック
基板において、前記電極は、中央部が厚さ５〜４０μｍ
の平坦面部であり外周端が全周にわたってくぼんだ曲面
から成る裾野状とされたメタライズ層の前記平坦面部上
に、上面の算術平均粗さが４〜８５μmであり、かつ前
記上面の外周端から側面にかけて全周にわたってなだら
かな曲面とされている銅層が積層されて成ることを特徴
とする。A ceramic substrate for a thermoelectric exchange module according to the present invention has a thermoelectric element in which a plurality of electrodes on which thermoelectric elements are mounted and fixed are independently formed on one main surface of the ceramic substrate. In the exchange module ceramic substrate, the central portion of the electrode has a thickness of 5 to 40 μm.
On the flat surface portion of the metallized layer which is a flat surface portion and has a skirt-shaped outer peripheral edge formed of a curved surface all around, the arithmetic average roughness of the upper surface is 4 to 85 μm, and from the outer peripheral edge of the upper surface. It is characterized in that it is formed by laminating a copper layer having a gentle curved surface all around the side surface.
【００１４】本発明は、上記の構成により、セラミック
基板と電極との熱膨張差により発生する熱応力、および
Ｃｕ層と熱電素子との熱膨張差により発生する熱応力を
十分に吸収し緩和させて、電極や熱電素子の剥がれを防
ぐことができる。その結果、光半導体素子等の発熱体か
ら発する熱を外部に効率良く伝達できる。According to the present invention, with the above structure, the thermal stress generated by the difference in thermal expansion between the ceramic substrate and the electrode and the thermal stress generated by the difference in thermal expansion between the Cu layer and the thermoelectric element are sufficiently absorbed and relaxed. As a result, peeling of the electrodes and thermoelectric elements can be prevented. As a result, the heat generated from the heating element such as the optical semiconductor element can be efficiently transmitted to the outside.
【００１５】本発明において、好ましくは、前記メタラ
イズ層の裾野状部の幅が５〜７０μｍであることを特徴
とする。In the present invention, preferably, the width of the bottom portion of the metallized layer is 5 to 70 μm.
【００１６】本発明は、上記の構成により、セラミック
基板と電極との熱膨張差により発生する熱応力を、より
十分に吸収緩和させ得、電極の剥がれを防ぐ効果がさら
に向上する。According to the present invention, with the above structure, the thermal stress generated by the difference in thermal expansion between the ceramic substrate and the electrode can be absorbed and relaxed more sufficiently, and the effect of preventing the electrode from peeling is further improved.
【００１７】[0017]
【発明の実施の形態】本発明の熱電交換モジュール用セ
ラミック基板を以下に詳細に説明する。図１および図２
は、本発明の熱電交換モジュール用セラミック基板につ
いて実施の形態の一例を示すものであり、図１は熱電交
換モジュール用セラミック基板の電極周辺部の断面図、
図２は図１の要部拡大断面図を示す。BEST MODE FOR CARRYING OUT THE INVENTION The ceramic substrate for a thermoelectric exchange module of the present invention will be described in detail below. 1 and 2
1 shows an example of an embodiment of a ceramic substrate for a thermoelectric exchange module of the present invention. FIG. 1 is a sectional view of an electrode peripheral portion of the ceramic substrate for a thermoelectric exchange module,
FIG. 2 shows an enlarged cross-sectional view of the main part of FIG.
【００１８】図１において、１はセラミック基板、２は
メタライズ層２ａと銅層２ｂとから成る電極、３は熱電
素子であり、これらセラミック基板１，電極２，熱電素
子３とで、光半導体素子等の発熱体が作動時に発する熱
を外部に効率良く伝える熱電交換モジュールが構成され
る。また、本発明の熱電交換モジュール用セラミック基
板は、セラミック基板１と電極２とにより構成される。In FIG. 1, 1 is a ceramic substrate, 2 is an electrode composed of a metallized layer 2a and a copper layer 2b, 3 is a thermoelectric element, and these ceramic substrate 1, electrode 2 and thermoelectric element 3 are optical semiconductor elements. The thermoelectric exchange module is configured to efficiently transfer the heat generated by the heating element such as the like to the outside. The ceramic substrate for thermoelectric exchange module of the present invention is composed of the ceramic substrate 1 and the electrode 2.
【００１９】セラミック基板１は、アルミナ（Ａｌ
2Ｏ3）セラミックスや窒化アルミニウム（ＡｌＮ）セラ
ミックス等のセラミックスから成り、その作製方法は、
原料粉末に適当な有機バインダや溶剤等を添加混合しペ
ースト状と成すとともに、このペーストをドクターブレ
ード法やカレンダーロール法によってセラミックグリー
ンシートと成し、しかる後セラミックグリーンシートに
適当な打ち抜き加工を施し、これを約１６００℃の高温
で焼結する方法である。The ceramic substrate 1 is made of alumina (Al
2 O 3 ) ceramics, aluminum nitride (AlN) ceramics, and other ceramics.
A suitable organic binder, solvent, etc. are added to the raw material powder and mixed to form a paste, and this paste is formed into a ceramic green sheet by the doctor blade method or calendar roll method, and then the ceramic green sheet is appropriately punched. This is a method of sintering this at a high temperature of about 1600 ° C.
【００２０】セラミック基板１の一方の主面には、ペル
チェ効果を利用してセラミック基板１を高温側または低
温側にするための、電圧印加用の複数の電極２が形成さ
れる。これらの電極２はそれぞれ独立しており、電極２
は、中央部が厚さ５〜４０μｍの平坦面部であり外周端
が全周にわたってくぼんだ曲面から成る裾野状とされた
メタライズ層２ａの平坦面部上に、上面の算術平均粗さ
が４〜８５μmであり、かつ上面の外周端から側面にか
けて全周にわたってなだらかな曲面とされているCｕ層
２ｂが積層されて成る。このような電極２は、例えば以
下の工程［１］〜［４］のようにして作製される。A plurality of electrodes 2 for voltage application are formed on one main surface of the ceramic substrate 1 to bring the ceramic substrate 1 to the high temperature side or the low temperature side by utilizing the Peltier effect. These electrodes 2 are independent of each other.
Is a flat surface portion having a thickness of 5 to 40 μm in the central portion and a skirt-shaped metallized layer 2a formed of a curved surface whose outer peripheral edge is indented all around, and the arithmetic average roughness of the upper surface is 4 to 85 μm. In addition, the Cu layer 2b having a smooth curved surface is laminated over the entire circumference from the outer peripheral edge of the upper surface to the side surface. Such an electrode 2 is manufactured, for example, by the following steps [1] to [4].
【００２１】［１］セラミック基板１の一方の主面に、
メタライズ層２ａと成るＷ，Ｍｏ，Ｍｎ等の粉末に有機
溶剤，溶媒を添加混合して得た金属ペーストを、予め従
来周知のスクリーン印刷法により５〜４０μｍの厚さで
全面に印刷塗布し、約１３００℃の高温で焼結する。[1] On one main surface of the ceramic substrate 1,
A metal paste obtained by adding and mixing an organic solvent and a solvent to powders of W, Mo, Mn, etc., which will be the metallized layer 2a, is printed and applied in advance to a thickness of 5 to 40 μm by a conventionally known screen printing method, Sinter at a high temperature of about 1300 ° C.
【００２２】［２］焼結した金属ペーストの上面に、Ｃ
ｕ層２ｂを形成しない部位にメッキレジストを約３００
μｍ程度の厚さで施した後、電解Ｃｕメッキをメッキレ
ジストの高さ（厚さ）よりも低い位置まで被着させ、そ
の後メッキレジストを剥離する。この工程により、全面
がメタライズ層２ａから成る上面に、複数の独立したＣ
ｕ層２ｂが形成されることとなる。[2] On the upper surface of the sintered metal paste, C
Approximately 300 plating resist is applied to the area where the u layer 2b is not formed.
After applying a thickness of about μm, electrolytic Cu plating is applied to a position lower than the height (thickness) of the plating resist, and then the plating resist is peeled off. By this step, a plurality of independent C's are formed on the upper surface entirely formed of the metallized layer 2a.
The u layer 2b is formed.
【００２３】［３］複数の独立したＣｕ層２ｂの周縁下
端の周辺部のみにメタライズ層２ａが残存するように、
即ちＣｕ層２ｂが互いに電気的に絶縁されるように、お
よびＣｕ層２ｂの上面の算術平均粗さが４〜８５μｍと
なるように、さらに熱電素子３が載置固定される上面の
平坦面部の外周側の外周端が全周にわたってなだらかな
曲面となるように、それぞれのＣｕ層２ｂ間のメタライ
ズ層２ａとＣｕ層２ｂ上面と外周端周辺部とをブラスト
研磨する。ブラスト研磨は、ブラスト材がＡｌ 2Ｏ3，Ｓ
ｉＣ等のセラミック粉から成り、その粒径は約２５μｍ
程度、ノズル距離１００ｍｍ，噴射圧力０．３ＭＰａ
（メガパスカル），噴射量１６０ｇ／分，ノズル移動速
度５０ｍｍ／秒の条件により吹き付けることにより行わ
れる。[3] Under the periphery of a plurality of independent Cu layers 2b
So that the metallized layer 2a remains only in the peripheral portion of the edge,
That is, the Cu layer 2b should be electrically insulated from each other.
And the arithmetic average roughness of the upper surface of the Cu layer 2b is 4 to 85 μm.
So that the thermoelectric element 3 is placed and fixed on the upper surface.
The outer peripheral edge on the outer peripheral side of the flat surface is gentle over the entire circumference
The metal layers between the Cu layers 2b should be curved to form curved surfaces.
Blasting the upper surfaces of the copper layer 2a, the Cu layer 2b, and the periphery of the outer peripheral edge.
Grind. For blast polishing, the blast material is Al 2O3, S
It is made of ceramic powder such as iC and has a particle size of about 25 μm.
Degree, nozzle distance 100mm, injection pressure 0.3MPa
(Megapascal), injection amount 160g / min, nozzle moving speed
Performed by spraying under conditions of 50 mm / sec.
Be done.
【００２４】［４］その後、水洗によりブラスト材を洗
浄し乾燥する。[4] After that, the blast material is washed with water and dried.
【００２５】電極２のメタライズ層２ａは、その外周端
が全周にわたってくぼんだ曲面から成る裾野状とされて
いるため、即ち、メタライズ層２ａの外周端が外側に向
かって凸もしくはセラミック基板１に対してほぼ垂直な
面とはならないため、ペルチェ効果によりセラミック基
板１が高温となっても、セラミック基板１とＣｕ層２ｂ
との間の熱膨張差により発生した熱応力を十分に吸収し
緩和させ得る。そのため、セラミック基板１とメタライ
ズ層２ａとの間で剥がれが発生しない。その結果、発熱
体が作動時に発する熱を外部に効率良く伝達し、発熱体
の作動性を非常に良好なものとし得る。The metallized layer 2a of the electrode 2 has a skirt shape in which the outer peripheral edge is formed of a curved surface which is concave over the entire circumference, that is, the outer peripheral edge of the metallized layer 2a is convex outward or is formed on the ceramic substrate 1. Since the surface is not substantially vertical to the ceramic substrate 1, even if the temperature of the ceramic substrate 1 becomes high due to the Peltier effect, the ceramic substrate 1 and the Cu layer 2b
The thermal stress generated by the difference in thermal expansion between and can be sufficiently absorbed and relaxed. Therefore, peeling does not occur between the ceramic substrate 1 and the metallized layer 2a. As a result, the heat generated by the heating element can be efficiently transmitted to the outside, and the operability of the heating element can be made very good.
【００２６】なお、メタライズ層２ａの中央部の厚さが
５μｍ未満の場合、厚さが非常に薄いため、メタライズ
層２ａの外周端をくぼんだ曲面から成る裾野状とするこ
とが困難であり、また焼結後にメタライズ層２ａ中にボ
イド（空孔）等が発生しセラミック基板１との接合強度
を十分なものとし難いという問題点がある。一方、４０
μｍを超える場合、熱電交換モジュールの高さが高くな
り、近時の熱電交換モジュールの小型軽量化といった動
向から外れる。また、この場合、熱伝導率がそれほど高
くないメタライズ層２ａの厚さを厚くすることとなるた
め、発熱体の作動時における熱の伝達性が低下するとい
う問題点がある。When the central portion of the metallized layer 2a has a thickness of less than 5 μm, the metallized layer 2a is so thin that it is difficult to form the outer peripheral edge of the metallized layer 2a into a skirt shape having a concave surface. Further, there is a problem that voids (holes) are generated in the metallized layer 2a after sintering and it is difficult to make the bonding strength with the ceramic substrate 1 sufficient. On the other hand, 40
When the thickness exceeds μm, the height of the thermoelectric exchange module becomes high, which deviates from the recent trend toward smaller and lighter thermoelectric exchange modules. Further, in this case, since the metallized layer 2a having a not so high thermal conductivity is thickened, there is a problem that the heat transfer property during the operation of the heating element is lowered.
【００２７】また、電極２は、Ｃｕ層２ｂの高さが５〜
３００μｍ程度の場合に十分に熱応力を吸収し緩和させ
る機能を発揮できる。５μｍ未満では、熱伝導性の低下
や電気抵抗の上昇により、大きな電流を流すことが困難
になる。一方、３００μｍを超えると、セラミック基板
１とＣｕ層２ｂとの間に発生する熱膨張差による熱応力
をメタライズ層２ａが十分に吸収し緩和させ難くなる。In the electrode 2, the height of the Cu layer 2b is 5 to 5.
When the thickness is about 300 μm, the function of sufficiently absorbing and relaxing the thermal stress can be exhibited. If the thickness is less than 5 μm, it becomes difficult to flow a large current due to a decrease in thermal conductivity and an increase in electric resistance. On the other hand, when the thickness exceeds 300 μm, the metallized layer 2a does not sufficiently absorb and relax the thermal stress due to the difference in thermal expansion between the ceramic substrate 1 and the Cu layer 2b.
【００２８】また、上記ブラスト研磨により、メタライ
ズ層２ａの裾野状部の幅を５〜７０μｍとすることがよ
く、その場合、セラミック基板１とＣｕ層２ｂとの間の
熱膨張差により発生した熱応力を、より十分に吸収し緩
和させ得る。裾野状部の幅が５μｍ未満の場合、大きな
電流を流すために、熱伝導性の向上や電気抵抗の低下を
目的として、特にＣｕ層２ｂの高さを３００〜５００μ
ｍ程度とした際、熱応力を十分に吸収し緩和させること
が困難となる。Further, the width of the skirt portion of the metallized layer 2a is preferably set to 5 to 70 μm by the blast polishing, and in this case, the heat generated by the difference in thermal expansion between the ceramic substrate 1 and the Cu layer 2b is used. The stress can be absorbed and relaxed more sufficiently. When the width of the skirt portion is less than 5 μm, in order to flow a large current, the height of the Cu layer 2b is set to 300 to 500 μm for the purpose of improving thermal conductivity and lowering electrical resistance.
When it is set to about m, it becomes difficult to absorb and relax the thermal stress sufficiently.
【００２９】一方、メタライズ層２ａの裾野状部の幅が
７０μｍを超えると、近接する電極２との電気的な絶縁
を十分なものとできないといった問題点が発生する。即
ち、電気的な絶縁を十分なものとするために各々の電極
２の間隔を大きくすると、近時の熱電交換モジュールの
小型軽量化といった動向から外れる。従って、特にＣｕ
層２ｂの高さを３００〜５００μｍ程度まで高くする場
合、裾野状部の幅を５〜７０μｍ程度としておくことが
良い。On the other hand, if the width of the skirt portion of the metallized layer 2a exceeds 70 μm, there arises a problem that the electrical insulation from the adjacent electrode 2 cannot be made sufficient. That is, if the distance between the electrodes 2 is increased in order to obtain sufficient electric insulation, the trend of downsizing and weight saving of the thermoelectric exchange module in recent years is deviated. Therefore, especially Cu
When increasing the height of the layer 2b to about 300 to 500 μm, it is preferable to set the width of the skirt portion to about 5 to 70 μm.
【００３０】また、電極２間の間隔は０．１〜２ｍｍが
よく、０．１ｍｍ未満では間隔が狭すぎるため、メタラ
イズ層２ａ同士が接触し電気的に接続されてしまう場合
がある。一方、２ｍｍを超えると、熱電交換モジュール
が大型化する。The distance between the electrodes 2 is preferably 0.1 to 2 mm. If the distance is less than 0.1 mm, the distance is too small, and the metallized layers 2a may come into contact with each other to be electrically connected. On the other hand, when it exceeds 2 mm, the thermoelectric exchange module becomes large.
【００３１】また、Ｃｕ層２ｂは、ブラスト研磨によ
り、Ｃｕ層２ｂの上面の算出平均粗さが４〜８５μｍに
形成される。このときＣｕ層２ｂの上面の算出平均粗さ
が４μｍ未満では、Ｃｕ層２ｂ上面の状態がなめらか過
ぎて、Ｃｕ層２ｂと熱電素子３とを接合する際の半田が
流れすぎることになる。そのため、両者を接合する半田
の端部の形状が凹んだ円弧状等のくぼんだ曲面状のメニ
スカス形状となり難いため、Ｃｕ層２ｂと熱電素子３と
の間に発生する熱応力によって剥がれが発生し易くな
る。The Cu layer 2b is formed by blasting so that the calculated average roughness of the upper surface of the Cu layer 2b is 4 to 85 μm. At this time, if the calculated average roughness of the upper surface of the Cu layer 2b is less than 4 μm, the state of the upper surface of the Cu layer 2b will be too smooth, and the solder at the time of joining the Cu layer 2b and the thermoelectric element 3 will flow too much. Therefore, since it is difficult for the end portion of the solder that joins them to have a concave meniscus shape such as a concave arc shape, peeling occurs due to the thermal stress generated between the Cu layer 2b and the thermoelectric element 3. It will be easier.
【００３２】一方、Ｃｕ層２ｂの上面の算出平均粗さが
８５μｍを超えると、Ｃｕ層２ｂ上面の凹凸が大き過ぎ
て、熱電素子３を接合するための半田の内部やＣｕ層２
ｂと熱電素子３との界面にボイド（空孔）が発生しやす
くなる。その結果、Ｃｕ層２ｂと熱電素子３とを半田接
合し熱電交換モジュールとした後、発熱体を作動させた
際の熱が熱電素子３からＣｕ層２ｂにかけて効率良く伝
わらないため、発熱体の作動性が低下し熱交換モジュー
ルの性能が確保され難くなる。On the other hand, when the calculated average roughness of the upper surface of the Cu layer 2b exceeds 85 μm, the unevenness on the upper surface of the Cu layer 2b is too large and the inside of the solder for joining the thermoelectric element 3 and the Cu layer 2 are too large.
Voids (holes) are likely to occur at the interface between b and the thermoelectric element 3. As a result, after the Cu layer 2b and the thermoelectric element 3 are soldered to each other to form a thermoelectric exchange module, the heat generated when the heating element is operated is not efficiently transferred from the thermoelectric element 3 to the Cu layer 2b. Performance deteriorates, and it becomes difficult to ensure the performance of the heat exchange module.
【００３３】また、Ｃｕ層２ｂは、ブラスト研磨によ
り、熱電素子３が載置固定される上面の中央部より外周
側には、外周端から側面にかけて全周にわたってなだら
かな曲面とされた曲面状部２ｂ−Ａが形成される。曲面
状部２ｂ−Ａは、熱膨張係数が約１７ｐｐｍ／℃（×１
０-6／℃）のＣｕ層２ｂと熱膨張係数が約１９ｐｐｍ／
℃の熱電素子３とを半田接合し熱電交換モジュールとし
た後、発熱体を作動させた際の熱による熱膨張差により
発生する熱応力による剥がれを有効に防止する機能を有
する。Further, the Cu layer 2b is formed by blasting into a curved surface portion which has a gentle curved surface over the entire circumference from the outer peripheral edge to the side surface on the outer peripheral side from the central portion of the upper surface on which the thermoelectric element 3 is mounted and fixed. 2b-A is formed. The curved portion 2b-A has a thermal expansion coefficient of about 17 ppm / ° C. (× 1
Cu layer 2b and the coefficient of thermal expansion of 0 -6 / ° C.) of about 19 ppm /
It has a function of effectively preventing peeling due to thermal stress generated due to a difference in thermal expansion due to heat when the heating element is operated after soldering the thermoelectric element 3 having a temperature of 3 ° C. to form a thermoelectric exchange module.
【００３４】Ｃｕ層２ｂと熱電素子３とを接合する半田
は、熱電素子３の下端側面から曲面状部２ｂ−Ａの上側
周辺部にかけて、適度なボリュームから成るとともに全
周にわたって凹んだ円弧状等のくぼんだ曲面から成るメ
ニスカスを形成し、かつ曲面状部２ｂ−Ａの下側周辺部
を全周にわたって囲むように接合される。このことか
ら、半田のメニスカスがＣｕ層２ｂと熱電素子３との間
に発生する熱応力を十分に吸収し緩和させ得るととも
に、曲面状部２ｂ−Ａの下側周辺部を囲む半田がＣｕ層
２ｂと熱電素子３との間に発生する熱応力を十分に抑制
させ得る。The solder for joining the Cu layer 2b and the thermoelectric element 3 has an appropriate volume from the lower end side surface of the thermoelectric element 3 to the upper peripheral portion of the curved surface portion 2b-A, and has an arc shape which is recessed all around. A meniscus having a concave curved surface is formed and the lower peripheral portion of the curved surface portion 2b-A is joined so as to surround the entire circumference. From this, the meniscus of the solder can sufficiently absorb and relax the thermal stress generated between the Cu layer 2b and the thermoelectric element 3, and the solder surrounding the lower peripheral portion of the curved surface portion 2b-A is the Cu layer. Thermal stress generated between 2b and the thermoelectric element 3 can be sufficiently suppressed.
【００３５】また、曲面状部２ｂ−Ａの曲率半径は５〜
１００μｍであることが好ましく、５μｍ未満の場合、
熱電素子３の側面下端から曲面状部２ｂ−Ａにかけて接
合される半田は、全周にわたって凹んだ円弧状等のくぼ
んだ曲面から成るメニスカス形状となり難くなる。その
ため、Ｃｕ層２ｂと熱電素子３との間に発生する熱応力
を十分に吸収し緩和させ難い。１００μｍを超えると、
曲面状部２ｂ−Ａの下側周辺部を全周にわたって囲むよ
うに半田が形成されない場合がある。そのため、Ｃｕ層
２ｂと熱電素子３との間に発生する熱応力を十分に抑制
させ難い。The radius of curvature of the curved portion 2b-A is 5 to 5.
100 μm is preferable, and when less than 5 μm,
The solder joined from the lower end of the side surface of the thermoelectric element 3 to the curved surface portion 2b-A is unlikely to have a meniscus shape having a concave curved surface such as an arc shape recessed over the entire circumference. Therefore, it is difficult to sufficiently absorb and relax the thermal stress generated between the Cu layer 2b and the thermoelectric element 3. If it exceeds 100 μm,
The solder may not be formed so as to surround the lower peripheral portion of the curved surface portion 2b-A over the entire circumference. Therefore, it is difficult to sufficiently suppress the thermal stress generated between the Cu layer 2b and the thermoelectric element 3.
【００３６】このようなメタライズ層２ａ，Ｃｕ層２ｂ
から成る電極２の上面には、酸化防止および半田接合性
を向上させるためにＮｉメッキ層，Ａｕメッキ層が順次
被着されているのがよく、Ｓｎ−Ａｇ系，Ｓｎ−Ｓｂ
系，Ｓｎ−Ｂｉ系，Ｓｎ−Ｐｂ系等の半田を介して、ｐ
型，ｎ型の熱電素子３が固着される。熱電素子３として
は、Ｂｉ2Ｔｅ3，ＰｂＴｅ等の金属間化合物や、Ｓｉ−
Ｇｅ系合金、Ｂｉ−Ｔｅ系合金等を用いる。また、熱電
素子３と電極２との接合を強固なものとするために、熱
電素子３の表面にＮｉメッキ層，Ｓｎメッキ層，半田メ
ッキ層等を被着させておいても良い。Such metallized layer 2a and Cu layer 2b
It is preferable that a Ni plating layer and an Au plating layer are sequentially deposited on the upper surface of the electrode 2 made of, for the purpose of preventing oxidation and improving solder jointability. Sn-Ag system, Sn-Sb
Via a solder such as Sn, Bi, Sn-Pb, etc.
Type and n-type thermoelectric elements 3 are fixed. As the thermoelectric element 3, an intermetallic compound such as Bi 2 Te 3 or PbTe or Si-
A Ge-based alloy, a Bi-Te-based alloy, or the like is used. Further, in order to strengthen the bond between the thermoelectric element 3 and the electrode 2, a Ni plating layer, a Sn plating layer, a solder plating layer or the like may be adhered to the surface of the thermoelectric element 3.
【００３７】さらに、熱電素子３の下面側のセラミック
基板１が高温端の場合、熱電素子３の上面側に電極の形
成されたセラミック基板１を低温端として接合すること
により、外部の発熱体の作動時に発する熱を低温端のセ
ラミック基板１から熱電素子３を介して高温端のセラミ
ック基板１、そして外部へと効率良く伝えることのでき
る熱電交換モジュールが作製できる。Further, when the ceramic substrate 1 on the lower surface side of the thermoelectric element 3 has a high temperature end, the ceramic substrate 1 having electrodes formed on the upper surface side of the thermoelectric element 3 is bonded as a low temperature end, so that the external heating element A thermoelectric exchange module capable of efficiently transmitting heat generated during operation from the ceramic substrate 1 at the low temperature end to the ceramic substrate 1 at the high temperature end via the thermoelectric element 3 and to the outside can be manufactured.
【００３８】本発明の熱電交換モジュール用セラミック
基板において、具体的には、図４に示した従来例のメタ
ライズ層１０２ｂの垂直上方への引っ張り強度（ピール
強度）は約４．９Ｎ／ｃｍ2であったのに対して、本発
明のメタライズ層２ｂの垂直上方への引っ張り強度は約
１４．７Ｎ／ｃｍ2と非常に大きいものであった。In the ceramic substrate for a thermoelectric exchange module of the present invention, specifically, the conventional metallization layer 102b shown in FIG. 4 has a vertical tensile strength (peel strength) of about 4.9 N / cm 2 . On the other hand, the tensile strength of the metallized layer 2b of the present invention in the vertically upward direction was very large, about 14.7 N / cm 2 .
【００３９】また、本発明の小型軽量の熱電交換モジュ
ールは、その上面に非常に発熱量の大きい発熱体を載置
固定し作動させた場合でも、本発明の電極を有する熱電
交換モジュール用セラミック基板により、発熱体から発
せられる熱を低温端のセラミック基板から熱電素子、電
極、セラミック基板を介して外部に効率良く放散し得る
信頼性の非常に高いものとなる。Further, the small and lightweight thermoelectric exchange module of the present invention has the ceramic substrate for a thermoelectric exchange module having the electrode of the present invention even when a heating element having a very large calorific value is mounted and fixed on the upper surface of the heating element. As a result, the heat generated from the heating element can be efficiently dissipated from the ceramic substrate at the low temperature end to the outside through the thermoelectric element, the electrode, and the ceramic substrate, which is highly reliable.
【００４０】なお、本発明は上記実施の形態に限定され
るものではなく、本発明の要旨を逸脱しない範囲内にお
いて種々の変更を施すことは何等差し支えない。The present invention is not limited to the above embodiment, and various modifications may be made without departing from the scope of the present invention.
【００４１】[0041]
【発明の効果】本発明は、熱電交換モジュール用セラミ
ック基板の電極は、中央部が厚さ５〜４０μｍの平坦面
部であり外周端が全周にわたってくぼんだ曲面から成る
裾野状とされたメタライズ層の平坦面部上に、上面の算
術平均粗さが４〜８５μmであり、かつ上面の外周端か
ら側面にかけて全周にわたってなだらかな曲面とされて
いる銅層が積層されて成ることにより、メタライズ層の
熱電素子に対する接合強度が大幅に増大し、セラミック
基板の電極と熱電素子の熱膨張差により発生する熱応力
を十分に吸収し緩和し得る。その結果、熱サイクルによ
り電極の剥離等が発生することが殆どなくなるととも
に、銅層と熱電素子とを接合する半田のメニスカスが銅
層と熱電素子との間に発生する熱応力を十分に吸収し緩
和させ得、かつ曲面状部の下側周辺部を囲む半田が銅層
と熱電素子との間に発生する熱応力を十分に抑制させ得
る。従って、熱電交換モジュールの上面に載置固定され
た発熱体の発する熱量が非常に大きい場合であっても、
セラミック基板と電極との熱膨張差により発生する熱応
力や、電極と熱電素子との熱膨張差により発生する熱応
力を十分に吸収し緩和できる。そのため、発熱体の発す
る熱を外部に効率良く伝達させ、発熱体の作動性を非常
に良好なものとできる。According to the present invention, an electrode of a ceramic substrate for a thermoelectric exchange module has a metallized layer in the form of a skirt formed of a flat surface portion having a thickness of 5 to 40 μm at its central portion and an indented curved surface at its outer peripheral edge. Of the metallized layer by laminating a copper layer having an arithmetic average roughness of 4 to 85 μm on the flat surface of and having a smooth curved surface from the outer peripheral edge to the side surface of the upper surface. The bonding strength with respect to the thermoelectric element is significantly increased, and the thermal stress generated by the difference in thermal expansion between the electrode of the ceramic substrate and the thermoelectric element can be sufficiently absorbed and relaxed. As a result, the peeling of the electrodes due to the thermal cycle hardly occurs, and the meniscus of the solder that joins the copper layer and the thermoelectric element sufficiently absorbs the thermal stress generated between the copper layer and the thermoelectric element. The solder that surrounds the lower peripheral portion of the curved surface portion can be relaxed, and the thermal stress generated between the copper layer and the thermoelectric element can be sufficiently suppressed. Therefore, even when the amount of heat generated by the heating element mounted and fixed on the upper surface of the thermoelectric exchange module is very large,
The thermal stress generated by the difference in thermal expansion between the ceramic substrate and the electrode and the thermal stress generated by the difference in thermal expansion between the electrode and the thermoelectric element can be sufficiently absorbed and relaxed. Therefore, the heat generated by the heating element can be efficiently transmitted to the outside, and the operability of the heating element can be made very good.
【００４２】また本発明は、好ましくはメタライズ層の
裾野状部の幅を５〜７０μｍとすることにより、セラミ
ック基板と電極との熱膨張差により発生する熱応力を、
より十分に吸収し緩和し得る。また、例えば、大電流を
流してペルチェ効果をさらに発揮させるために、熱伝導
性の向上や電気抵抗の低下を目的として、銅層を３００
〜５００μｍ程度まで厚くした場合であっても、セラミ
ック基板と電極との熱膨張差により発生する熱応力を十
分に吸収し緩和することができる。その結果、発熱体の
発する熱を外部に効率良く伝達させ、発熱体の作動性を
非常に良好なものとできる。Further, according to the present invention, preferably, the width of the skirt portion of the metallized layer is set to 5 to 70 μm so that the thermal stress generated by the difference in thermal expansion between the ceramic substrate and the electrode is reduced.
Can absorb and relax more fully. Further, for example, in order to further exert a Peltier effect by passing a large current, a copper layer of 300 is formed for the purpose of improving thermal conductivity and lowering electrical resistance.
Even when the thickness is increased to about 500 μm, the thermal stress generated by the difference in thermal expansion between the ceramic substrate and the electrodes can be sufficiently absorbed and relaxed. As a result, the heat generated by the heating element can be efficiently transmitted to the outside, and the operability of the heating element can be made very good.
【図１】本発明の熱電交換モジュール用セラミック基板
について実施の形態の一例を示す電極周辺部の断面図で
ある。FIG. 1 is a cross-sectional view of an electrode peripheral portion showing an example of an embodiment of a ceramic substrate for a thermoelectric exchange module of the present invention.
【図２】図１の熱電交換モジュール用セラミック基板の
電極の要部拡大断面図である。FIG. 2 is an enlarged cross-sectional view of a main part of an electrode of the ceramic substrate for thermoelectric exchange module of FIG.
【図３】従来の熱電交換モジュール用セラミック基板の
電極周辺部の断面図である。FIG. 3 is a sectional view of an electrode peripheral portion of a conventional ceramic substrate for a thermoelectric exchange module.
【図４】（ａ）は図３の電極周辺部の拡大断面図であ
り、（ｂ）は（ａ）の電極の要部拡大断面図である。4A is an enlarged cross-sectional view of a peripheral portion of the electrode of FIG. 3, and FIG. 4B is an enlarged cross-sectional view of a main part of the electrode of FIG.
１：セラミック基板 ２：電極 ２ａ：メタライズ層 ２ｂ：銅層 ２ｂ−Ａ：曲面状部 ３：熱電素子 1: Ceramic substrate 2: Electrode 2a: Metallized layer 2b: Copper layer 2b-A: curved portion 3: Thermoelectric element
Claims (2)
熱電素子が載置固定される電極がそれぞれ独立して複数
形成された熱電交換モジュール用セラミック基板におい
て、前記電極は、中央部が厚さ５〜４０μｍの平坦面部
であり外周端が全周にわたってくぼんだ曲面から成る裾
野状とされたメタライズ層の前記平坦面部上に、上面の
算術平均粗さが４〜８５μmであり、かつ前記上面の外
周端から側面にかけて全周にわたってなだらかな曲面と
されている銅層が積層されて成ることを特徴とする熱電
交換モジュール用セラミック基板。1. A ceramic substrate for a thermoelectric exchange module, wherein a plurality of electrodes on which thermoelectric elements are mounted and fixed are independently formed on one main surface of a ceramic substrate, wherein the central portion of the electrode is thick. On the flat surface portion of the metallized layer which is a flat surface portion having a size of 5 to 40 μm and whose outer peripheral edge is a concave curved surface over the entire circumference, the arithmetic average roughness of the upper surface is 4 to 85 μm, and the upper surface. A ceramic substrate for a thermoelectric exchange module, characterized in that it is formed by laminating copper layers having a gentle curved surface over the entire circumference from the outer peripheral edge to the side surface.
７０μｍであることを特徴とする請求項１記載の熱電交
換モジュール用セラミック基板。2. The width of the bottom portion of the metallized layer is 5 to 5.
It is 70 micrometers, The ceramic substrate for thermoelectric exchange modules of Claim 1 characterized by the above-mentioned.
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|---|---|---|---|
| JP2001257611A JP4313964B2 (en) | 2001-08-28 | 2001-08-28 | Ceramic substrate for thermoelectric exchange module |
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| Publication Number | Publication Date |
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| JP4313964B2 JP4313964B2 (en) | 2009-08-12 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2017204550A (en) * | 2016-05-11 | 2017-11-16 | 積水化学工業株式会社 | Thermoelectric conversion material, thermoelectric conversion element and method of manufacturing thermoelectric conversion element |
| JP2022119182A (en) * | 2021-02-03 | 2022-08-16 | 三菱マテリアル株式会社 | Thermoelectric conversion module, and, manufacturing method for thermoelectric conversion module |
-
2001
- 2001-08-28 JP JP2001257611A patent/JP4313964B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2017204550A (en) * | 2016-05-11 | 2017-11-16 | 積水化学工業株式会社 | Thermoelectric conversion material, thermoelectric conversion element and method of manufacturing thermoelectric conversion element |
| JP2022119182A (en) * | 2021-02-03 | 2022-08-16 | 三菱マテリアル株式会社 | Thermoelectric conversion module, and, manufacturing method for thermoelectric conversion module |
| JP7248091B2 (en) | 2021-02-03 | 2023-03-29 | 三菱マテリアル株式会社 | Thermoelectric conversion module and method for manufacturing thermoelectric conversion module |
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| Publication number | Publication date |
|---|---|
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