JP4124150B2 - Thermoelectric module manufacturing method - Google Patents

Thermoelectric module manufacturing method Download PDF

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JP4124150B2
JP4124150B2 JP2004090621A JP2004090621A JP4124150B2 JP 4124150 B2 JP4124150 B2 JP 4124150B2 JP 2004090621 A JP2004090621 A JP 2004090621A JP 2004090621 A JP2004090621 A JP 2004090621A JP 4124150 B2 JP4124150 B2 JP 4124150B2
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thermoelectric material
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JP2005277222A (en
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幸俊 鈴木
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Yamaha Corp
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本発明は、ペルチェ効果を利用した電子冷却及びゼーベック効果を利用した熱電発電等に使用される熱電モジュールの製造方法に関する。   The present invention relates to a method of manufacturing a thermoelectric module used for electronic cooling using the Peltier effect and thermoelectric power generation using the Seebeck effect.

ペルチェ効果又はゼーベック効果を利用した熱電モジュールは、構造が簡単で小型化及び軽量化が容易であり、更に、無音及び無振動で動作し、メンテナンスが不要であることから、特殊な用途向けの小型冷蔵庫、半導体レーザ等の半導体装置内部の温度調節器及び発電装置等、様々な分野への適用が検討されている。   Thermoelectric modules using the Peltier effect or Seebeck effect are simple in structure, easy to reduce in size and weight, operate silently and without vibration, and require no maintenance. Application to various fields such as a temperature controller and a power generator inside a semiconductor device such as a refrigerator or a semiconductor laser is being studied.

図１５は従来の熱電モジュールの製造方法の一例を示すフローチャート図である。図１５に示すように、従来の熱電モジュール１００の製造方法は、主に、熱電素子１０２を製造する材料加工工程と、下側基板１０６ａ及び上側基板１０６ｂを製造する基板工程と、これらを組み立てる組み立て工程とからなる。材料加工工程では、先ず、ＢｉＴｅ系等の半導体熱電材料のインゴット１０１を作製する（ステップ１０１ａ）。次に、このインゴット１０１を素子の長さに相当する厚さの円盤状にスライシングし、熱電材料のウエハ１０１ａを切り出す（ステップ１０２ａ）。この熱電材料のウエハ１０１ａの表面に、良好なハンダ付け性を得るためのＮｉめっきを施し（ステップ１０３ａ）、このＮｉめっきが施された熱電材料のウエハ１０１ｂを升目状にダイシングして熱電素子１０２にする（ステップ１０４ａ）。このようにして、向かい合う２面にのみＮｉめっき層が形成された熱電素子１０２を製造する。この熱電素子１０２は、原料インゴットを形成する半導体熱電材料の組成を調整することによって、ｐ型熱電素子１０２ｐ又はｎ型熱電素子１０２ｎとすることができる。   FIG. 15 is a flowchart showing an example of a conventional method for manufacturing a thermoelectric module. As shown in FIG. 15, the conventional method for manufacturing the thermoelectric module 100 mainly includes a material processing step for manufacturing the thermoelectric element 102, a substrate step for manufacturing the lower substrate 106a and the upper substrate 106b, and an assembly for assembling them. Process. In the material processing step, first, an ingot 101 of a semiconductor thermoelectric material such as BiTe is manufactured (step 101a). Next, the ingot 101 is sliced into a disk having a thickness corresponding to the length of the element, and a wafer 101a of thermoelectric material is cut out (step 102a). The surface of this thermoelectric material wafer 101a is subjected to Ni plating for obtaining good solderability (step 103a), and the thermoelectric material wafer 101b on which this Ni plating has been applied is diced into a grid shape to thermoelectric element 102. (Step 104a). In this way, the thermoelectric element 102 in which the Ni plating layer is formed only on the two faces facing each other is manufactured. The thermoelectric element 102 can be a p-type thermoelectric element 102p or an n-type thermoelectric element 102n by adjusting the composition of the semiconductor thermoelectric material forming the raw material ingot.

一方、基板工程では、先ず、１対のセラミックス基板１０３を用意し（ステップ１０１ｂ）、これらのセラミックス基板１０３上の熱電素子搭載部分をメタライズして下部電極又は上部電極となるＣｕ電極１０４を形成する（ステップ１０２ｂ）。その後、このＣｕ電極１０４上にＮｉめっき層１０５を形成して基板１０６とする（ステップ１０３ｂ）。このようにして、下部電極が形成された下側基板１０６ａ及び上部電極が形成された上側基板１０６ｂが製造される。   On the other hand, in the substrate process, first, a pair of ceramic substrates 103 are prepared (step 101b), and the thermoelectric element mounting portions on these ceramic substrates 103 are metallized to form a Cu electrode 104 to be a lower electrode or an upper electrode. (Step 102b). Thereafter, a Ni plating layer 105 is formed on the Cu electrode 104 to form a substrate 106 (step 103b). In this way, the lower substrate 106a on which the lower electrode is formed and the upper substrate 106b on which the upper electrode is formed are manufactured.

次に、組み立て工程として、下側基板１０６ａの下部電極上に、前述の材料加工工程において製造されたｐ型熱電素子１０２ｐ及びｎ型熱電素子１０２ｎを交互に配置し、ｐ型熱電素子１０２ｐ及びｎ型熱電素子１０２ｎのＮｉめっき層形成面と下部電極とをはんだにより接合する（ステップ１０５）。また、ｐ型熱電素子１０２ｐ及びｎ型熱電素子１０２ｎのＮｉめっき層が形成された他の面と上部電極とをはんだにより接合する（ステップ１０６）。このとき、隣り合う１対の下部電極上に配置された熱電素子のうち、隣り合うｐ型熱電素子１０２ｐ及びｎ型熱電素子１０２ｎを１つの上部電極に接合することにより、複数のｐ型熱電素子１０２ｐ及びｎ型熱電素子１０２ｎを直列に接続する。更に、下部電極及び上部電極により直列接続された熱電素子のうち、端部に配置された熱電素子が接合されている下部電極にリードを接続し（ステップ１０７）、熱電モジュール１００の製造を完了する。   Next, as an assembly process, the p-type thermoelectric elements 102p and the n-type thermoelectric elements 102n manufactured in the above-described material processing process are alternately arranged on the lower electrode of the lower substrate 106a, and the p-type thermoelectric elements 102p and n The Ni plating layer forming surface of the mold thermoelectric element 102n and the lower electrode are joined by solder (step 105). Further, the other surface of the p-type thermoelectric element 102p and the n-type thermoelectric element 102n on which the Ni plating layer is formed and the upper electrode are joined by solder (step 106). At this time, among the thermoelectric elements arranged on a pair of adjacent lower electrodes, adjacent p-type thermoelectric elements 102p and n-type thermoelectric elements 102n are joined to one upper electrode, thereby a plurality of p-type thermoelectric elements. 102p and n-type thermoelectric element 102n are connected in series. Further, among the thermoelectric elements connected in series by the lower electrode and the upper electrode, the lead is connected to the lower electrode to which the thermoelectric element arranged at the end is joined (step 107), and the manufacture of the thermoelectric module 100 is completed. .

このように、従来の熱電モジュール１００の製造方法においては、下側基板１０６ａの下部電極上に、ｐ型熱電素子１０２ｐとｎ型熱電素子１０２ｎとを交互に配置しなければならないため、この素子の配列作業に時間を要していた。また、従来の熱電モジュール１００の製造方法は、組み立て工程において熱電素子を１個ずつ取り扱うため、素子の大きさが小さくなると、その取扱いが難しくなり、実装機で掴めなくなったり、掴んだときに熱電素子が欠けてしまったりすることがあり、作業効率及び歩留まりが低下する。   Thus, in the conventional method for manufacturing the thermoelectric module 100, the p-type thermoelectric elements 102p and the n-type thermoelectric elements 102n must be alternately arranged on the lower electrode of the lower substrate 106a. It took time to arrange. In addition, since the conventional method for manufacturing the thermoelectric module 100 handles thermoelectric elements one by one in the assembly process, if the size of the element becomes small, it becomes difficult to handle the thermoelectric module 100. The device may be chipped, resulting in a decrease in work efficiency and yield.

そこで、生産性、機械的強度及び切り代によるロスを改善し、切断時の割れ及び欠け並びに配置ミス等を防止すると共に熱電素子の小型化を実現するため、ｎ型熱電素子とｐ型熱電素子とが絶縁材を介して接合された熱電素子集積体を形成し、この熱電素子集積板と各電極とを接合する方法が提案されている（例えば、特許文献１乃至５参照）。図１６は特許文献１に記載の熱電素子集積体を示す斜視図である。なお、図１６においては、ｐ型熱電材料とｎ型熱電材料とを区別するために、図中に「ｐ」及び「ｎ」の符号を付しており、以下の図においても同様である。図１６に示すように、特許文献１には、ドクターブレード法等により絶縁材１１３を介してシート状のｐ型熱電材料１１１及びｎ型熱電材料１１２を交互に積層した後、焼結して熱電素子集積体にする方法が開示されている。   Therefore, in order to improve productivity, mechanical strength and loss due to cutting allowance, prevent cracks and chips during cutting, misplacement, etc., and realize miniaturization of the thermoelectric element, an n-type thermoelectric element and a p-type thermoelectric element Has been proposed in which a thermoelectric element integrated body is formed by bonding them with an insulating material, and the thermoelectric element integrated plate and each electrode are bonded (see, for example, Patent Documents 1 to 5). FIG. 16 is a perspective view showing a thermoelectric element integrated body described in Patent Document 1. FIG. In FIG. 16, in order to distinguish between the p-type thermoelectric material and the n-type thermoelectric material, reference numerals “p” and “n” are given in the figure, and the same applies to the following figures. As shown in FIG. 16, in Patent Document 1, a sheet-shaped p-type thermoelectric material 111 and an n-type thermoelectric material 112 are alternately stacked via an insulating material 113 by a doctor blade method or the like, and then sintered and thermoelectrically processed. A method of forming an element integration is disclosed.

図１７は特許文献２に記載の熱電素子集積体を示す斜視図であり、図１８は特許文献３に記載の熱電素子集積体を示す斜視図である。図１７に示すように、特許文献２に記載の熱電素子の製造方法においては、板状のｎ型熱電材料１１５と絶縁材１１７とを交互に積層し、これを積層面に対して垂直に切断したｎ型積層体と、板状のｐ型熱電材料１１６と絶縁材１１７とを交互に積層し、これを積層面に対して垂直に切断したｐ型積層体とを、絶縁材１１７を挟みながら交互に積層して熱電素子集積体としている。一方、図１８に示すように、特許文献３に記載の熱電素子の製造方法においては、板状のｎ型熱電材料１１５及びｐ型熱電材料１１６を断熱材１１８を挟んで交互に積層し、これを積層面に対して垂直に切断した積層体と断熱材１１８とを交互に積層して熱電素子積層体としている。   FIG. 17 is a perspective view showing a thermoelectric element assembly described in Patent Document 2, and FIG. 18 is a perspective view showing a thermoelectric element assembly described in Patent Document 3. As shown in FIG. 17, in the method for manufacturing a thermoelectric element described in Patent Document 2, plate-like n-type thermoelectric materials 115 and insulating materials 117 are alternately stacked and cut perpendicularly to the stacking surface. N-type laminates, and p-type laminates obtained by alternately laminating plate-like p-type thermoelectric materials 116 and insulating materials 117 and cutting them perpendicular to the laminated surface, with the insulating materials 117 sandwiched between them. The thermoelectric element integrated body is formed by alternately laminating. On the other hand, as shown in FIG. 18, in the method for manufacturing a thermoelectric element described in Patent Document 3, plate-like n-type thermoelectric materials 115 and p-type thermoelectric materials 116 are alternately stacked with a heat insulating material 118 interposed therebetween. The thermoelectric element laminate is formed by alternately laminating laminates obtained by cutting the layers perpendicular to the laminate surface and the heat insulating material 118.

図１９（ａ）乃至（ｄ）は特許文献４に記載の熱電素子の製造方法をその工程順に示す斜視図である。特許文献４に記載の熱電素子の製造方法においては、先ず、図１９（ａ）に示すように、板状のｐ型熱電材料１２１とｎ型熱電材料１２２とを断熱材１２３を挟んで交互に積層する。次に、図１９（ｂ）に示すように、積層方向に対して垂直な方向に溝を形成した後、図１９（ｃ）に示すように、連結部を残して溝を形成した部分を切り離す。そして、溝に断熱材１２３を充填した後、図１９（ｄ）に示すように、連結部を切断除去して熱電素子集積体としている。   19 (a) to 19 (d) are perspective views showing the manufacturing method of the thermoelectric element described in Patent Document 4 in the order of the steps. In the method for manufacturing a thermoelectric element described in Patent Document 4, first, as shown in FIG. 19A, a plate-shaped p-type thermoelectric material 121 and an n-type thermoelectric material 122 are alternately arranged with a heat insulating material 123 interposed therebetween. Laminate. Next, as shown in FIG. 19 (b), after forming grooves in a direction perpendicular to the stacking direction, as shown in FIG. . And after filling the groove | channel with the heat insulating material 123, as shown in FIG.19 (d), the connection part is cut and removed and it is set as the thermoelectric element integrated body.

図２０（ａ）及び（ｂ）は特許文献５に記載の熱電モジュールの製造方法をその工程順に示す斜視図である。特許文献５に記載の熱電モジュールの製造方法においては、先ず、図２０（ａ）に示すように、ｐ型熱電材料の棒材１２５とｎ型熱電材料の棒材１２６とをスペーサ１２７を介して交互に接合した後、この接合体を各棒材の長手方向に垂直な方向に切断する。そして、図２０（ｂ）に示すように、切断した部材を一列おきに切断面に沿ってずらして配置すると共に、各部材の間にスペーサ１２７を挿入して接合し、隣接する熱電材料の縦及び横方向が全て逆導電型の熱電素子集積体としている。   20 (a) and 20 (b) are perspective views showing the method of manufacturing the thermoelectric module described in Patent Document 5 in the order of the steps. In the method for manufacturing a thermoelectric module described in Patent Document 5, first, as shown in FIG. 20A, a p-type thermoelectric material rod 125 and an n-type thermoelectric material rod 126 are interposed via a spacer 127. After alternately joining, this joined body is cut in a direction perpendicular to the longitudinal direction of each bar. Then, as shown in FIG. 20 (b), the cut members are arranged so as to be shifted along the cut surface in every other row, and the spacers 127 are inserted and joined between the members, and the vertical portions of the adjacent thermoelectric materials are arranged. In addition, the horizontal direction is a reverse conductivity type thermoelectric element integrated body.

特開平１１−１２１８１５号公報JP-A-11-121815 特開平８−２２２７７０号公報JP-A-8-222770 特開昭６３−２０８８１号公報JP-A-63-20881 特開昭６３−２０８８０号公報JP 63-20880 A 特開２００２−１１１０８４号公報JP 2002-111084 A

しかしながら、前述の従来の技術には以下に示す問題点がある。即ち、特許文献１に記載の熱電素子積層体は、焼成により収縮するため、モジュール化する際に素子が電極上からずれてしまうという問題点がある。また、特許文献１乃至４に記載の熱電素子積層体は、ｎ型熱電材料とｐ型熱電材料とを交互にマトリクス状に配置していないため、モジュール化する際に斜めに配線しなければならず、電極が細長くなって抵抗が大きくなるという問題点がある。更に、特許文献５に記載の熱電素子積層体は、熱電材料の棒材を使用しているため折れやすく、取扱いが難しいと共に、切断した部材を一列おきに切断面に沿ってずらして配置しているため、無駄になる部分があるという問題点がある。更にまた、特許文献１乃至５に記載の熱電素子積層体のように、各熱電材料間に絶縁材及び断熱材が設けられていると、熱伝導により熱冷電極間の断熱が十分にとれないという問題点がある。   However, the conventional techniques described above have the following problems. That is, since the thermoelectric element laminate described in Patent Document 1 shrinks by firing, there is a problem that the element is displaced from the electrode when modularized. Moreover, since the thermoelectric element laminated body of patent documents 1 thru | or 4 does not arrange | position n type thermoelectric material and p type thermoelectric material alternately in matrix form, when it modularizes, it must wire diagonally. However, there is a problem that the electrode becomes elongated and the resistance increases. Furthermore, the thermoelectric element laminate described in Patent Document 5 is easy to break because it uses a bar of a thermoelectric material, and it is difficult to handle, and the cut members are arranged by shifting along the cut surface every other row. Therefore, there is a problem that there is a wasteful part. Furthermore, when the insulating material and the heat insulating material are provided between the thermoelectric materials as in the thermoelectric element laminated body described in Patent Documents 1 to 5, the heat insulation between the hot and cold electrodes cannot be sufficiently obtained due to heat conduction. There is a problem.

本発明はかかる問題点に鑑みてなされたものであって、熱電素子の配列を容易に行うことができ、従来よりも製造コストを低減することができる熱電モジュールの製造方法を提供することを目的とする。   The present invention has been made in view of such problems, and it is an object of the present invention to provide a method of manufacturing a thermoelectric module that can easily arrange thermoelectric elements and can reduce the manufacturing cost as compared with the related art. And

本願第１発明に係る熱電モジュールの製造方法は、基板上の各下部電極上に夫々１対のｐ型熱電素子及びｎ型熱電素子が配置され、隣接する１対の下部電極に配置されたｐ型熱電素子及びｎ型熱電素子のうち隣接するｐ型熱電素子及びｎ型熱電素子が１個の上部電極に接合されている熱電モジュールの製造方法において、ｐ型熱電材料及びｎ型熱電材料を所定の間隔で切断してｐ型熱電材料及びｎ型熱電材料のウエハを得る工程と、前記ｐ型熱電材料のウエハと前記ｎ型熱電材料のウエハと交互に配置しそれらの間にアルカリ性溶剤に可溶な熱硬化性樹脂シートからなる第１のスペーサを挿入して相互に接合して熱電材料積層体を得る工程と、この熱電材料積層体を所定の間隔で積層方向に切断して長尺のｐ型熱電材料及びｎ型熱電材料が夫々前記第１のスペーサを介して積層した積層部材を得る工程と、切断後の各積層部材を隣接する積層部材間でｐ型熱電材料とｎ型熱電材料とが対向するように１枚おきに切断面における面内方向に１８０°回転させて配置しそれらの間にアルカリ性溶剤に可溶な熱硬化性樹脂シートからなる第２のスペーサを挿入して相互に接合して一体化する工程と、この一体化した部材を所定の間隔で前記ｐ型熱電材料及びｎ型熱電材料の長手方向に直交する方向に切断して熱電素子集積体を得る工程と、この熱電素子集積体の下面を構成する熱電素子集積体の一方の切断面上に、隣接する１対のｐ型熱電材料及びｎ型熱電材料毎に１個となるように、下部電極を形成すると共に、隣接する下部電極のうち一方の下部電極に接触するｐ型熱電素子と他方の下部電極に接触するｎ型熱電素子とが１個の上部電極により接続されるようにして、前記熱電素子集積体の上面を構成する熱電素子集積体の他方の切断面上に複数個の上部電極を形成する工程と、前記熱電素子集積体と下部基板とを前記下部電極を介して接合する工程と、前記第１及び第２のスペーサをアルカリ性溶剤により溶解させて除去する工程と、を有することを特徴とする。 In the method of manufacturing the thermoelectric module according to the first invention of the present application, a pair of p-type thermoelectric elements and n-type thermoelectric elements are arranged on each lower electrode on the substrate, and p is arranged on a pair of adjacent lower electrodes. In a manufacturing method of a thermoelectric module in which adjacent p-type thermoelectric elements and n-type thermoelectric elements of a p-type thermoelectric element and an n-type thermoelectric element are joined to one upper electrode, the p-type thermoelectric material and the n-type thermoelectric material are predetermined. A p-type thermoelectric material wafer and an n-type thermoelectric material wafer obtained by cutting at intervals, and the p-type thermoelectric material wafer and the n-type thermoelectric material wafer are alternately arranged, and an alkaline solvent is allowed between them. Inserting a first spacer made of a molten thermosetting resin sheet and joining them together to obtain a thermoelectric material laminate, and cutting the thermoelectric material laminate at a predetermined interval in the laminating direction p-type thermoelectric material and n-type thermoelectric material A step of obtaining a laminated member laminated via the first spacer, and cutting every other laminated member so that the p-type thermoelectric material and the n-type thermoelectric material face each other between the laminated members adjacent to each other And a step of inserting a second spacer made of a thermosetting resin sheet soluble in an alkaline solvent and joining them together to integrate them by rotating 180 ° in the in-plane direction on the surface, Cutting the integrated member at a predetermined interval in a direction perpendicular to the longitudinal direction of the p-type thermoelectric material and the n-type thermoelectric material to obtain a thermoelectric element integrated body; and a thermoelectric element constituting the lower surface of the thermoelectric element integrated body on one cut surface of the element stack, such that one each p-type thermoelectric material and the n-type thermoelectric material adjacent pair, to form a lower electrode, the lower part of one of the adjacent lower electrodes P-type thermoelectric element in contact with the electrode and under the other A plurality of upper electrodes are formed on the other cut surface of the thermoelectric element assembly constituting the upper surface of the thermoelectric element assembly so that the n-type thermoelectric element in contact with the partial electrode is connected by one upper electrode. A step of bonding the thermoelectric element assembly and the lower substrate through the lower electrode, and a step of dissolving and removing the first and second spacers with an alkaline solvent. It is characterized by that.

本発明においては、ｐ型熱電素子及びｎ型熱電素子がスペーサを介して交互にマトリクス状に配置されている熱電素子集積体を基板上に配置するだけで、ｐ型熱電素子及びｎ型熱電素子を基板上に交互にマトリクス状に配置することができる。これにより、素子の取扱い性が向上すると共に、各素子の配置が容易になり、素子の誤配置を防止することができる。更に、製造時間の短縮化及び製造工程の簡略化を実現することができるため、製造コストを低減することができる。   In the present invention, a p-type thermoelectric element and an n-type thermoelectric element can be obtained simply by arranging on a substrate a thermoelectric element assembly in which p-type thermoelectric elements and n-type thermoelectric elements are alternately arranged in a matrix via spacers. Can be alternately arranged in a matrix on the substrate. Thereby, the handleability of the elements is improved, the arrangement of each element is facilitated, and the misplacement of the elements can be prevented. Further, since the manufacturing time can be shortened and the manufacturing process can be simplified, the manufacturing cost can be reduced.

本願第２発明に係る熱電モジュールの製造方法は、基板上の各下部電極上に夫々１対のｐ型熱電素子及びｎ型熱電素子が配置され、隣接する１対の下部電極に配置されたｐ型熱電素子及びｎ型熱電素子のうち隣接するｐ型熱電素子及びｎ型熱電素子が１個の上部電極に接合されている熱電モジュールの製造方法において、ｐ型熱電材料及びｎ型熱電材料を所定の間隔で切断してｐ型熱電材料及びｎ型熱電材料のウエハを得る工程と、前記ｐ型熱電材料のウエハと前記ｎ型熱電材料のウエハと交互に配置しそれらの間にアルカリ性溶剤に可溶な熱硬化性樹脂シートからなる第１のスペーサを挿入して相互に接合して熱電材料積層体を得る工程と、この熱電材料積層体を所定の間隔で積層方向に切断して長尺のｐ型熱電材料及びｎ型熱電材料が夫々前記第１のスペーサを介して積層した積層部材を得る工程と、切断後の各積層部材を隣接する積層部材間でｐ型熱電材料とｎ型熱電材料とが対向するように１枚おきに切断面における面内方向に１８０°回転させて配置しそれらの間にアルカリ性溶剤に可溶な熱硬化性樹脂シートからなる第２のスペーサを挿入して相互に接合して一体化する工程と、この一体化した部材を所定の間隔で前記ｐ型熱電材料及びｎ型熱電材料の長手方向に直交する方向に切断して熱電素子集積体を得る工程と、この熱電素子集積体の下面を構成する熱電素子集積体の一方の切断面上に、隣接する１対のｐ型熱電材料及びｎ型熱電材料毎に１個となるように、下部電極を形成すると共に、隣接する下部電極のうち一方の下部電極に接触するｐ型熱電素子と他方の下部電極に接触するｎ型熱電素子とが１個の上部電極により接続されるようにして、前記熱電素子集積体の上面を構成する熱電素子集積体の他方の切断面上に複数個の上部電極を形成する工程と、前記熱電素子集積体と下部基板及び上部基板とを前記下部電極及び上部電極を介して接合する工程と、前記第１及び第２のスペーサをアルカリ性溶剤により溶解させて除去する工程と、を有することを特徴とする。 In the method for manufacturing a thermoelectric module according to the second invention of the present application, a pair of p-type thermoelectric elements and n-type thermoelectric elements are arranged on each lower electrode on the substrate, and p is arranged on a pair of adjacent lower electrodes. In a manufacturing method of a thermoelectric module in which adjacent p-type thermoelectric elements and n-type thermoelectric elements of a p-type thermoelectric element and an n-type thermoelectric element are joined to one upper electrode, the p-type thermoelectric material and the n-type thermoelectric material are predetermined. A p-type thermoelectric material wafer and an n-type thermoelectric material wafer obtained by cutting at intervals, and the p-type thermoelectric material wafer and the n-type thermoelectric material wafer are alternately arranged, and an alkaline solvent is allowed between them. Inserting a first spacer made of a molten thermosetting resin sheet and joining them together to obtain a thermoelectric material laminate, and cutting the thermoelectric material laminate at a predetermined interval in the laminating direction p-type thermoelectric material and n-type thermoelectric material A step of obtaining a laminated member laminated via the first spacer, and cutting every other laminated member so that the p-type thermoelectric material and the n-type thermoelectric material face each other between the laminated members adjacent to each other And a step of inserting a second spacer made of a thermosetting resin sheet soluble in an alkaline solvent and joining them together to integrate them by rotating 180 ° in the in-plane direction on the surface, Cutting the integrated member at a predetermined interval in a direction perpendicular to the longitudinal direction of the p-type thermoelectric material and the n-type thermoelectric material to obtain a thermoelectric element integrated body; and a thermoelectric element constituting the lower surface of the thermoelectric element integrated body A lower electrode is formed on one cut surface of the element integrated body so that there is one for each pair of adjacent p-type thermoelectric material and n-type thermoelectric material. P-type thermoelectric element in contact with electrode and under the other And n-type thermoelectric elements in contact with the part electrodes so as to be connected by a single upper electrode, a plurality of upper electrodes on the other cut surface of the thermoelectric element stack which constitutes the upper surface of the thermoelectric element stack A step of bonding the thermoelectric element assembly to the lower substrate and the upper substrate through the lower electrode and the upper electrode, and removing the first and second spacers by dissolving them with an alkaline solvent. And a step of performing.

また、熱電材料の積層体を得る工程において、ｐ型熱電材料のウエハ及び前記ｎ型熱電材料のウエハに第１のスペーサを積層し接合してもよく、更に、一体化する工程において、前記切断後の各積層部材に第２のスペーサを積層し接合してもよい。これにより、スペーサのずれによる積層不良を防止することができると共に、界面への気泡の混入、即ち、泡かみを防止することができる。更にまた、この第１及び第２のスペーサとしては、例えば、ドライフィルムレジストを使用することができる。 Further, in the step of obtaining a laminate of the thermoelectric material may be laminated to first spacer wafer and the wafer of the n-type thermoelectric material of the p-type thermoelectric material junctions, further, in the step of integrating, the cutting A second spacer may be laminated and bonded to each subsequent laminated member. As a result, it is possible to prevent stacking faults due to spacer displacement, and it is possible to prevent bubbles from entering the interface, that is, foaming. Furthermore, as the first and second spacers, for example, a dry film resist can be used.

本発明によれば、ｐ型熱電素子及びｎ型熱電素子がスペーサを介して交互にマトリクス状に配置されている熱電素子集積体を基板上に接合するため、これらの素子を容易に配置することができると共に、製造時間の短縮化及び製造工程の簡略化を実現することができるため製造コストを低減することができる。   According to the present invention, since a thermoelectric element assembly in which p-type thermoelectric elements and n-type thermoelectric elements are alternately arranged in a matrix via spacers is bonded onto a substrate, these elements can be easily arranged. The manufacturing cost can be reduced because the manufacturing time can be shortened and the manufacturing process can be simplified.

以下、本発明の実施形態に係る熱電モジュールの製造方法について添付の図面を参照して具体的に説明する。図１（ａ）は本実施形態の熱電モジュール１０を示す斜視図であり、図１（ｂ）はその断面図である。なお、図１（ａ）においては、ｐ型熱電素子とｎ型熱電素子とを区別するために、図中に「ｐ」及び「ｎ」の符号を付する。図１（ａ）及び（ｂ）に示すように、本実施形態の熱電モジュール１０は、セラミックス等の絶縁性の材料からなり一方の面上に下部電極７ａが形成された下側基板８と、セラミックス等の絶縁性の材料からなり一方の面上に上部電極７ｂが形成された上側基板９とが、下部電極７ａと上部電極７ｂとが対向するように配置されている。そして、下部電極７ａ及び上部電極７ｂ間には、ｐ型熱電素子１ｐ及びｎ型熱電素子２ｎが交互に配置されており、下部電極７ａ上に配置されたｐ型熱電素子１ｐ及びｎ型熱電素子２ｎからなる１対の熱電素子のｐ型熱電素子１ｐと、この下部電極７ａと隣り合う他の下部電極７ａ上に配置された１対の熱電素子のｎ型熱電素子２ｎとを、１個の上部電極７ｂに接合することにより、複数個のｐ型熱電素子１ｐ及びｎ型熱電素子２ｎが直列に接続されている。また、この直列接続体の両端部の熱電素子が接合された下部電極７ａには、夫々リード線１１ａ及び１１ｂがはんだ等により接合されている。   Hereinafter, a method for manufacturing a thermoelectric module according to an embodiment of the present invention will be specifically described with reference to the accompanying drawings. FIG. 1A is a perspective view showing a thermoelectric module 10 of the present embodiment, and FIG. 1B is a cross-sectional view thereof. In FIG. 1A, in order to distinguish a p-type thermoelectric element and an n-type thermoelectric element, reference numerals “p” and “n” are given in the figure. As shown in FIGS. 1A and 1B, the thermoelectric module 10 of this embodiment includes a lower substrate 8 made of an insulating material such as ceramics and having a lower electrode 7a formed on one surface thereof, An upper substrate 9 made of an insulating material such as ceramics and having an upper electrode 7b formed on one surface is disposed so that the lower electrode 7a and the upper electrode 7b face each other. And between the lower electrode 7a and the upper electrode 7b, the p-type thermoelectric element 1p and the n-type thermoelectric element 2n are alternately arranged, and the p-type thermoelectric element 1p and the n-type thermoelectric element arranged on the lower electrode 7a. A pair of thermoelectric elements p-type thermoelectric element 1p composed of 2n, and a pair of thermoelectric element n-type thermoelectric elements 2n arranged on another lower electrode 7a adjacent to the lower electrode 7a. A plurality of p-type thermoelectric elements 1p and n-type thermoelectric elements 2n are connected in series by bonding to the upper electrode 7b. Further, lead wires 11a and 11b are joined to the lower electrode 7a to which the thermoelectric elements at both ends of the series connection body are joined by solder or the like.

次に、本実施形態の熱電モジュール１０の製造方法について説明する。図２は本実施形態の熱電モジュールの製造方法を示すフローチャート図である。また、図３乃至１３は本実施形態の熱電モジュールの製造方法をその工程順に示す図である。本実施形態の熱電モジュールの製造方法においては、先ず、図３に示すように、所定の厚さにスライスされたｐ型熱電材料ウエハ１及びｎ型熱電材料ウエハ２の表面に、ドライフィルムレジスト等のように、両面に接着性がありアルカリに可溶な熱硬化型樹脂シートからなるスペーサ３をラミネートする。このとき、ｐ型熱電材料ウエハ１及びｎ型熱電材料ウエハ２の一方の面にスペーサ３をラミネートしても、ｐ型熱電材料ウエハ１又はｎ型熱電材料ウエハ２のいずれか一方の両面にスペーサ３をラミネートしてもよい。そして、ｐ型熱電材料ウエハ１とｎ型熱電材料ウエハ２とを交互に積層した後、加熱しながら加圧してｐ型及びｎ型熱電材料の積層体４を作製する（ステップ１）。   Next, the manufacturing method of the thermoelectric module 10 of this embodiment is demonstrated. FIG. 2 is a flowchart showing a method for manufacturing the thermoelectric module of the present embodiment. 3 to 13 are views showing the method of manufacturing the thermoelectric module of this embodiment in the order of the steps. In the thermoelectric module manufacturing method of the present embodiment, first, as shown in FIG. 3, a dry film resist or the like is formed on the surfaces of the p-type thermoelectric material wafer 1 and the n-type thermoelectric material wafer 2 sliced to a predetermined thickness. As described above, the spacer 3 made of a thermosetting resin sheet having adhesiveness on both sides and soluble in alkali is laminated. At this time, even if the spacer 3 is laminated on one surface of the p-type thermoelectric material wafer 1 and the n-type thermoelectric material wafer 2, the spacers are provided on both surfaces of either the p-type thermoelectric material wafer 1 or the n-type thermoelectric material wafer 2. 3 may be laminated. Then, after p-type thermoelectric material wafers 1 and n-type thermoelectric material wafers 2 are alternately laminated, the laminate 4 of p-type and n-type thermoelectric materials is produced by applying pressure while heating (step 1).

次に、図４に示すように、積層体４を積層方向に所定の間隔でスライスして、積層体ウエハ４ａにする（ステップＳ２）。この積層体ウエハ４ａの表面に、両面に接着性がありアルカリに可溶な熱硬化型樹脂シートからなるスペーサ３をラミネートした後、図５に示すように、隣接する積層体ウエハ４ａ間でｐ型熱電材料１ａとｎ型熱電材料２ａとが対向するように、複数枚の積層体ウエハ４ａを１枚おきに面内方向に１８０°回転させて配置する。これらを、加熱しながら加圧してｐ型熱電材料１ａ及びｎ型熱電材料２ａの集積体５を作製する（ステップＳ３）。次に、図６に示すように、この熱電材料の集積体５を、積層方向並びにｐ型熱電材料１ａ及びｎ型熱電材料２ａの長手方向に直交する方向に所定の間隔でスライスして、図７（ａ）及び（ｂ）に示すｐ型熱電素子１ｐ及びｎ型熱電素子２ｎがスペーサ３を介して交互にマトリクス状に配置されている熱電素子集積体５ａにする（ステップＳ４）。 Next, as shown in FIG. 4, is sliced in Jo Tokoro intervals laminate 4 in the stacking direction, and the laminate wafer 4a (step S2). After laminating a spacer 3 made of a thermosetting resin sheet having adhesiveness on both sides and soluble in alkali on the surface of the laminated wafer 4a, as shown in FIG. A plurality of laminated wafers 4a are alternately rotated 180 ° in the in-plane direction so that the type thermoelectric material 1a and the n-type thermoelectric material 2a face each other. These are pressurized while being heated to produce an integrated body 5 of the p-type thermoelectric material 1a and the n-type thermoelectric material 2a (step S3). Next, as shown in FIG. 6, this thermoelectric material assembly 5 is sliced at predetermined intervals in the stacking direction and in the direction orthogonal to the longitudinal direction of the p-type thermoelectric material 1a and the n-type thermoelectric material 2a. The p-type thermoelectric element 1p and the n-type thermoelectric element 2n shown in FIGS. 7 (a) and 7 (b) are formed into a thermoelectric element integrated body 5a alternately arranged in a matrix via the spacers 3 (step S4).

次に、図８（ａ）及び（ｂ）に示すように、レジスト６により、熱電素子集積体５ａの一方の面上に下部電極のパターンを、他方の面上に上部電極のパターンを形成する（ステップＳ５）。その後、図９（ａ）及び（ｂ）に示すように、熱電素子集積体５ａの両面に、めっき法などによりＣｕ等の電極材料からなる金属膜を形成する（ステップＳ６）。これにより、熱電素子集積体５ａの一方の面上に金属膜７ａが、他方の面上に金属膜７ｂが形成され、更に、レジスト６上には金属膜７ｃ及び金属膜７ｄが形成される。そして、図１０（ａ）及び（ｂ）に示すように、レジスト６をリフトオフすることにより、レジスト６上に形成された金属膜７ｃ及び金属膜７ｄが除去され、熱電素子集積体５ａの一方の面上に残った金属膜７ａが下部電極となり、他方の面上に残った金属膜７ｂが上部電極となる。（ステップＳ７）。   Next, as shown in FIGS. 8A and 8B, a resist 6 forms a lower electrode pattern on one surface of the thermoelectric element assembly 5a and an upper electrode pattern on the other surface. (Step S5). Thereafter, as shown in FIGS. 9A and 9B, a metal film made of an electrode material such as Cu is formed on both surfaces of the thermoelectric element integrated body 5a by plating or the like (step S6). As a result, a metal film 7 a is formed on one surface of the thermoelectric element assembly 5 a, a metal film 7 b is formed on the other surface, and a metal film 7 c and a metal film 7 d are formed on the resist 6. Then, as shown in FIGS. 10A and 10B, by lifting off the resist 6, the metal film 7c and the metal film 7d formed on the resist 6 are removed, and one of the thermoelectric element assemblies 5a is removed. The metal film 7a remaining on the surface becomes the lower electrode, and the metal film 7b remaining on the other surface becomes the upper electrode. (Step S7).

次に、図１１（ａ）及び（ｂ）に示すように、熱電素子集積体５ａの下部電極７ａが形成された面と下側基板８とを接合した後（ステップＳ８）、図１２（ａ）及び（ｂ）に示すように、熱電素子集積体５ａの上部電極７ｂが形成された面と上側基板９とを接合する（ステップＳ９）。そして、下側基板８及び上側基板９が接合された熱電素子集積体５ａのスペーサ３を、アルカリにより溶解して除去した後、図１３（ａ）及び（ｂ）に示すように、下側基板８及び上側基板９を切断して、モジュール毎に分離し、更に、リード線（図示せず）をはんだ付けして熱電モジュール１０とする（ステップＳ１０）。   Next, as shown in FIGS. 11A and 11B, after the surface on which the lower electrode 7a of the thermoelectric element assembly 5a is formed and the lower substrate 8 are joined (step S8), FIG. ) And (b), the surface of the thermoelectric element assembly 5a on which the upper electrode 7b is formed and the upper substrate 9 are joined (step S9). Then, after the spacer 3 of the thermoelectric element integrated body 5a to which the lower substrate 8 and the upper substrate 9 are joined is dissolved and removed with alkali, the lower substrate is formed as shown in FIGS. 13 (a) and 13 (b). 8 and the upper substrate 9 are cut and separated into modules, and lead wires (not shown) are soldered to form the thermoelectric module 10 (step S10).

次に、本実施形態の熱電モジュール１０の動作について説明する。この熱電モジュール１０においては、例えば、下部電極７ａ及び上部電極７ｂにより接続されたｐ型熱電素子１ｐ及び熱電素子２ｎに電流を流すと、電流はｎ型熱電素子２ｎの下側から上部電極７ｂを通ってｐ型熱電素子１ｐの下側へと流れる。一方、エネルギーはｐ型熱電素子１ｐでは電流と同じ方向に、ｎ型熱電素子２ｎでは電流と逆の方向へ移動するため、上部電極７ｂ側ではエネルギーが不足して温度が下がり（吸熱）下部電極７ａ側ではエネルギーが放出されて温度が上がる（放熱）。   Next, operation | movement of the thermoelectric module 10 of this embodiment is demonstrated. In this thermoelectric module 10, for example, when a current is passed through the p-type thermoelectric element 1p and the thermoelectric element 2n connected by the lower electrode 7a and the upper electrode 7b, the current flows from the lower side of the n-type thermoelectric element 2n to the upper electrode 7b. It flows through the p-type thermoelectric element 1p. On the other hand, the energy moves in the same direction as the current in the p-type thermoelectric element 1p, and in the opposite direction to the current in the n-type thermoelectric element 2n, so that the energy is insufficient on the upper electrode 7b side and the temperature drops (heat absorption). On the 7a side, energy is released and the temperature rises (heat dissipation).

本実施形態の熱電モジュールの製造方法においては、ｐ型熱電素子１ｐ及びｎ型熱電素子２ｎがスペーサ３を介して交互にマトリクス状に配置されている集積体の熱電素子集積体５ａを基板上に配置するだけで、ｐ型熱電素子１ｐ及びｎ型熱電素子２ｎを基板上に交互にマトリクス状に配置することができる。これにより、素子の取扱い性が向上すると共に、素子の配置が容易になり、素子の誤配置を防止することができる。更に、製造時間の短縮化及び製造工程の簡略化を実現することができるため、製造コストを低減することができる。   In the manufacturing method of the thermoelectric module of the present embodiment, the integrated thermoelectric element assembly 5a in which the p-type thermoelectric element 1p and the n-type thermoelectric element 2n are alternately arranged in a matrix via the spacer 3 is formed on the substrate. The p-type thermoelectric elements 1p and the n-type thermoelectric elements 2n can be alternately arranged in a matrix on the substrate simply by arranging them. Thereby, the handleability of the elements is improved, the arrangement of the elements is facilitated, and the misplacement of the elements can be prevented. Further, since the manufacturing time can be shortened and the manufacturing process can be simplified, the manufacturing cost can be reduced.

また、本実施形態の熱電モジュールの製造方法においては、ｐ型熱電材料のウエハ１及びｎ型熱電材料のウエハ２を積層した後スライスして積層体ウエハ４ａにする工程、及びこの積層体ウエハ４ａを１枚おきに面内方向に１８０°回転させながら積層した後スライスして熱電素子集積体５ａにする工程、即ち、積層及びスライスを２ずつ行うだけで、ｐ型熱電素子１ｐ及びｎ型熱電素子２ｎが交互にマトリクス状に配置された熱電素子集積体５ａを作製することができる。この積層工程においては、ウエハ状の熱電材料を使用するため、棒状の熱電材を使用するよりも取扱い性が優れている。また、積層体ウエハ４ａを１枚おきに１８０°回転させて積層することにより、ｐ型熱電素子１ｐ及びｎ型熱電素子２ｎを交互にマトリクス状に配置することができるため、無駄になる部分がない。その結果、従来の熱電モジュールの製造方法よりも、製造コストを低減することができる。   Moreover, in the manufacturing method of the thermoelectric module of the present embodiment, the p-type thermoelectric material wafer 1 and the n-type thermoelectric material wafer 2 are laminated and then sliced to obtain a laminated wafer 4a, and this laminated wafer 4a. Are laminated while rotating every other piece by 180 ° in the in-plane direction, and then sliced into the thermoelectric element integrated body 5a, that is, the lamination and slicing are performed two by two, so that the p-type thermoelectric element 1p and the n-type thermoelectric The thermoelectric element integrated body 5a in which the elements 2n are alternately arranged in a matrix can be manufactured. In this laminating step, since a wafer-like thermoelectric material is used, the handleability is superior to that of using a rod-like thermoelectric material. Also, by laminating every other laminated wafer 4a by 180 °, the p-type thermoelectric elements 1p and the n-type thermoelectric elements 2n can be alternately arranged in a matrix, so there is a wasteful part. Absent. As a result, the manufacturing cost can be reduced as compared with the conventional method for manufacturing a thermoelectric module.

更に、本実施形態の熱電モジュール１０は、ｐ型熱電素子１ｐ及びｎ型熱電素子２ｎ間のスペーサ３を除去しているため、ｐ型熱電素子１ｐ及びｎ型熱電素子２ｎ間の空気層により、下部電極７ａ及び上部電極７ｂ間の断熱性が高まり、ｐ型熱電素子１ｐ及びｎ型熱電素子２ｎ間に絶縁材又は断熱材が充填されている従来の熱電モジュールよりも性能を向上させることができる。   Furthermore, since the thermoelectric module 10 of this embodiment removes the spacer 3 between the p-type thermoelectric element 1p and the n-type thermoelectric element 2n, the air layer between the p-type thermoelectric element 1p and the n-type thermoelectric element 2n The heat insulation between the lower electrode 7a and the upper electrode 7b is enhanced, and the performance can be improved as compared with a conventional thermoelectric module in which an insulating material or a heat insulating material is filled between the p-type thermoelectric element 1p and the n-type thermoelectric element 2n. .

次に、本実施形態の熱電モジュール製造方法の変形例について説明する。図１４（ａ）は本実施形態の熱電モジュールの変形例を示す斜視図であり、図１４（ｂ）はその断面図である。前述の熱電モジュールの製造方法においては、下側基板８及び上側基板９が設けられた熱電モジュール１０の製造方法について述べたが、本発明はこれに限定されるものではなく、例えば、放熱側基板となる上側基板９がないスケルトンタイプの熱電モジュールにも適用することができ、同様の効果が得られる。スケルトンタイプの熱電モジュールの場合、前述のステップＳ９の後、下側基板８が接合された熱電素子集積体５ａのスペーサ３を、アルカリにより溶解して除去する。そして、図１４（ａ）及び（ｂ）に示すように、下側基板８を切断して、モジュール毎に分離し、更に、リード線（図示せず）をはんだ付けして熱電モジュール２０とする。   Next, a modified example of the thermoelectric module manufacturing method of the present embodiment will be described. FIG. 14A is a perspective view showing a modification of the thermoelectric module of the present embodiment, and FIG. 14B is a cross-sectional view thereof. In the above-described manufacturing method of the thermoelectric module, the manufacturing method of the thermoelectric module 10 provided with the lower substrate 8 and the upper substrate 9 has been described. However, the present invention is not limited to this, for example, the heat dissipation substrate. The present invention can also be applied to a skeleton type thermoelectric module without the upper substrate 9, and the same effect can be obtained. In the case of a skeleton type thermoelectric module, after step S9 described above, the spacer 3 of the thermoelectric element assembly 5a to which the lower substrate 8 is bonded is dissolved and removed by alkali. Then, as shown in FIGS. 14A and 14B, the lower substrate 8 is cut and separated for each module, and lead wires (not shown) are soldered to form the thermoelectric module 20. .

なお、本実施形態の熱電モジュールの製造方法においては、熱電素子集積体５ａの表面上にレジストパターンを形成した後、めっきを行い、リフトオフして各電極をパターニングしているが、本発明はこれに限定されるものではなく、例えば、レジストをパターニングする前に、熱電素子集積体５ａの表面全体に下地層を形成し、この下地層上にレジストパターンを形成し、レジストの開口部にめっきにより金属膜７を形成した後、レジストを除去すると共に露出した下地層を除去してもよい。又は、めっきを行う前に、レジストをマスクにして下地層をエッチングしてからめっきを行ってもよい。この場合、下地層がある部分にのみめっき膜が成長する。また、めっきを行う前にリフトオフ法により下地層をパターニングし、その後めっきを行うこともできる。この場合も、下地層がある部分にのみめっき膜が形成される。その他、レジスパターンを形成する前に下地層及び金属膜７を、熱電素子集積体５ａの表面全体に形成し、その後これらの積層膜をパターニングして各電極を形成する方法もある。   In the manufacturing method of the thermoelectric module of the present embodiment, after forming a resist pattern on the surface of the thermoelectric element assembly 5a, plating is performed and lift-off is performed to pattern each electrode. For example, before patterning the resist, a base layer is formed on the entire surface of the thermoelectric element assembly 5a, a resist pattern is formed on the base layer, and the resist openings are plated by plating. After forming the metal film 7, the resist may be removed and the exposed underlayer may be removed. Alternatively, before plating, the underlayer may be etched using a resist as a mask before plating. In this case, the plating film grows only in the portion where the underlayer is present. Alternatively, the underlayer can be patterned by a lift-off method before plating, and then plating can be performed. Also in this case, the plating film is formed only on the portion where the underlayer is present. In addition, there is a method in which the base layer and the metal film 7 are formed on the entire surface of the thermoelectric element integrated body 5a before the resist pattern is formed, and then these stacked films are patterned to form each electrode.

また、本実施形態の熱電モジュールの製造方法においては、下部電極７ａ及び上部電極７ｂを形成し、熱電素子集積体５ａに下側基板８及び上側基板９を接合した後、スペーサ３を除去しているが、本発明はこれに限定されるものではなく、例えば、一方の基板を接合した後スペーサ３を除去し、その後、他方の基板を接合してもよい。   In the method for manufacturing the thermoelectric module of the present embodiment, the lower electrode 7a and the upper electrode 7b are formed, the lower substrate 8 and the upper substrate 9 are joined to the thermoelectric element integrated body 5a, and then the spacer 3 is removed. However, the present invention is not limited to this, and for example, after joining one substrate, the spacer 3 may be removed, and then the other substrate may be joined.

更に、本実施形態の熱電モジュールの製造方法においては、下部電極７ａ及び上部電極７ｂが形成された熱電素子集積体５ａを基板に接合しているが、本発明はこれに限定されるものではなく、例えば、熱電素子集積体５ａ上には下地層のみを形成し、この下地層と基板上に形成された電極とを接合してもよい。この場合も、熱電素子集積体５ａに下側基板８及び上側基板９を接合した後、スペーサ３を除去する方法、及び、一方の基板を接合した後スペーサ３を除去し、その後他方の基板を接合する方法のいずれも適用することができる。   Furthermore, in the manufacturing method of the thermoelectric module of the present embodiment, the thermoelectric element integrated body 5a on which the lower electrode 7a and the upper electrode 7b are formed is bonded to the substrate, but the present invention is not limited to this. For example, only the base layer may be formed on the thermoelectric element integrated body 5a, and the base layer and the electrode formed on the substrate may be joined. Also in this case, after joining the lower substrate 8 and the upper substrate 9 to the thermoelectric element integrated body 5a, the spacer 3 is removed, and after joining one substrate, the spacer 3 is removed, and then the other substrate is attached. Any of the joining methods can be applied.

このように、本実施形態の熱電モジュールの製造方法においては、スペーサ３を除去する工程を、従来の熱電モジュールの製造方法よりも後の工程で行うため、製造工程におけるハンドリングによる破壊を防止し、歩留まりを向上することができる。   Thus, in the manufacturing method of the thermoelectric module of this embodiment, since the process of removing the spacer 3 is performed in a process subsequent to the manufacturing method of the conventional thermoelectric module, the destruction due to handling in the manufacturing process is prevented, Yield can be improved.

以下、本発明の実施例の効果について、本発明の範囲から外れる比較例と比較して説明する。先ず、本発明の実施例として、前述の実施形態と同様の方法で、熱電モジュールを作製した。本実施例においては、ｐ型熱電材料としてＢｉ０．４Ｓｂ１．６Ｔｅ３を使用し、ｎ型熱電材料としてＢｉ２．０Ｔｅ２．７Ｓｅ０．３にＨｇＢｒ２を０．０６質量％添加したものを使用した。これらｐ型及びｎ型熱電材料のインゴットをスライスして、厚さ９００μｍのｐ型及びｎ型熱電材料のウエハを作製した。そして、このｐ型及びｎ型熱電材料のウエハを、厚さが１００μｍのアクリル系ドライフィルムレジストを介して交互に積層した後、２９．４Ｎ／ｃｍ２で加圧しながら２００℃で３０分間加熱してアクリル系ドライフィルムレジストを硬化させ、ｐ型及びｎ型熱電材料の積層体を作製した。その後、この熱電材料の積層体を、ワイヤーソーにより積層方向に対して垂直な方向に切断して、厚さが９００μｍの積層体のウエハを作製した。 Hereinafter, the effect of the Example of this invention is demonstrated compared with the comparative example which remove | deviates from the scope of the present invention. First, as an example of the present invention, a thermoelectric module was manufactured by the same method as that of the above-described embodiment. In this example, Bi 0.4 Sb 1.6 Te 3 is used as the p-type thermoelectric material, and 0.06 mass of HgBr 2 is added to Bi 2.0 Te 2.7 Se 0.3 as the n-type thermoelectric material. % Added. The p-type and n-type thermoelectric material ingots were sliced to produce wafers of p-type and n-type thermoelectric materials having a thickness of 900 μm. Then, the p-type and n-type thermoelectric material wafers were alternately laminated through an acrylic dry film resist having a thickness of 100 μm, and then heated at 200 ° C. for 30 minutes while being pressurized at 29.4 N / cm 2. The acrylic dry film resist was cured to produce a laminate of p-type and n-type thermoelectric materials. Thereafter, the thermoelectric material laminate was cut with a wire saw in a direction perpendicular to the laminating direction to produce a laminated wafer having a thickness of 900 μm.

次に、この積層体のウエハを、１枚おきに上下を逆にし、厚さが１００μｍのアクリル系ドライフィルムレジストを介して複数枚積層した後、２９．４Ｎ／ｃｍ２で加圧しながら２００℃で３０分間加熱してアクリル系ドライフィルムレジストを硬化させ、ｐ型及びｎ型熱電材料が交互にマトリクス状に配置されている集積体を作製した。そして、この熱電材料の集積体を、ワイヤーソーにより積層方向に対して垂直で且つ各熱電材料の長手方向に対して垂直な方向に切断して、厚さが８１０μｍで、ｐ型及びｎ型熱電素子がアクリル系ドライフィルムレジストを介して交互にマトリクス状に配置されている集積体のウエハを作製した。 Next, every other wafer of this laminate was turned upside down, and a plurality of wafers were laminated via an acrylic dry film resist having a thickness of 100 μm, and then pressed at 29.4 N / cm 2 at 200 ° C. The acrylic dry film resist was cured by heating for 30 minutes to produce an integrated body in which p-type and n-type thermoelectric materials were alternately arranged in a matrix. Then, this thermoelectric material assembly is cut with a wire saw in a direction perpendicular to the stacking direction and perpendicular to the longitudinal direction of each thermoelectric material, and has a thickness of 810 μm, p-type and n-type thermoelectrics. An integrated wafer was fabricated in which elements were alternately arranged in a matrix via an acrylic dry film resist.

次に、この集積体のウエハの両面に、スパッタにより、厚さ２０００ÅのＣｕめっきシード層を形成した。その後、レジストにより、集積体のウエハの一方の面のＣｕめっきシード層上に下部電極のパターンを形成し、他方の面のＣｕめっきシード層上に上部電極のパターンを形成した。そして、集積体のウエハの両面に厚さ５０μｍのＣｕめっき層を形成した後、レジストを剥離し、更に、Ｃｕめっきシード層をエッチングにより除去して、集積体のウエハの一方の面に下部電極を、他方の面に上部電極を形成した。   Next, a Cu plating seed layer having a thickness of 2000 mm was formed on both surfaces of the wafer of the integrated body by sputtering. Thereafter, a resist pattern was formed on the Cu plating seed layer on one side of the wafer of the integrated body, and an upper electrode pattern was formed on the Cu plating seed layer on the other side. Then, after forming a Cu plating layer having a thickness of 50 μm on both surfaces of the wafer of the integrated body, the resist is peeled off, and further, the Cu plating seed layer is removed by etching, and a lower electrode is formed on one surface of the wafer of the integrated body. An upper electrode was formed on the other surface.

次に、集積体のウエハの下部電極と下側基板とを、上部部電極と上側基板と夫々接合した後、アルカリ性溶剤により、ｐ型及びｎ型熱電素子間のアクリル系ドライフィルムレジストを除去した。そして、ｐ型及びｎ型熱電素子の直列接続体の両端部の熱電素子が接合された下部電極に、夫々リード線をはんだにより接合した後、ダイシングして基板サイズが縦８ｍｍ、横１２ｍｍであり、熱電素子のサイズが縦０．９ｍｍ、横０．９ｍｍ、高さ０．８１ｍｍであり、熱電素子対が２６対である熱電モジュールを作製した。なお、本実施例の熱電モジュールの基板面積は９．６０×１０−５ｍ２、チップ総面積は４．２１×１０−５ｍ２、隙間面積は５．３９×１０−５ｍ２であった。 Next, after the lower electrode and the lower substrate of the integrated wafer were joined to the upper electrode and the upper substrate, respectively, the acrylic dry film resist between the p-type and n-type thermoelectric elements was removed with an alkaline solvent. . Then, after the lead wires are joined to the lower electrodes to which the thermoelectric elements at both ends of the series connection body of the p-type and n-type thermoelectric elements are joined by soldering, the substrate size is 8 mm in length and 12 mm in width. A thermoelectric module having a thermoelectric element size of 0.9 mm in length, 0.9 mm in width, and 0.81 mm in height, and 26 thermoelectric element pairs was produced. The substrate area of the thermoelectric module of this example was 9.60 × 10 −5 m 2 , the total chip area was 4.21 × 10 −5 m 2 , and the gap area was 5.39 × 10 −5 m 2. It was.

次に、本発明の比較例として、アクリル系ドライフィルムレジストを除去せず、それ以外は、前述の実施例の熱電モジュールと同様の方法及び条件で、ｐ型及びｎ型熱電素子間にドライフィルムレジストが充填されている熱電モジュールを作製した。本比較例の熱電モジュールにおいては、前述の実施例の熱電モジュールと同様に、基板サイズを縦８ｍｍ、横１２ｍｍ、熱電素子のサイズを縦０．９ｍｍ、横０．９ｍｍ、高さ０．８１ｍｍ、熱電素子対を２６対とした。なお、この熱電モジュールの基板面積は９．６０×１０−５ｍ２、チップ総面積は４．２１×１０−５ｍ２、隙間面積は５．３９×１０−５ｍ２であった。 Next, as a comparative example of the present invention, the acrylic dry film resist is not removed, and other than that, the dry film is formed between the p-type and n-type thermoelectric elements by the same method and conditions as the thermoelectric module of the above-mentioned embodiment A thermoelectric module filled with resist was produced. In the thermoelectric module of this comparative example, similarly to the thermoelectric module of the above-described embodiment, the substrate size is 8 mm long and 12 mm wide, the size of the thermoelectric element is 0.9 mm long, 0.9 mm wide, 0.81 mm high, There were 26 thermoelectric element pairs. The substrate area of this thermoelectric module was 9.60 × 10 −5 m 2 , the total chip area was 4.21 × 10 −5 m 2 , and the gap area was 5.39 × 10 −5 m 2 .

そして、上述の方法により作製された実施例及び比較例の熱電モジュールの性能を評価した。具体的には、各熱電モジュールに対し、高温側基板を１００℃に保ち、低温側基板の温度を測定しながら、高温側と低温側との温度差が最大になるように調節しながら電流を流し、各熱電モジュールが作り出せる最大温度差（ΔＴｍａｘ）を測定した。なお、最大温度差（ΔＴｍａｘ）の測定は、真空中で行った。 And the performance of the thermoelectric module of the Example and comparative example which were produced by the above-mentioned method was evaluated. Specifically, for each thermoelectric module, while maintaining the high temperature side substrate at 100 ° C. and measuring the temperature of the low temperature side substrate, the current is adjusted while adjusting the temperature difference between the high temperature side and the low temperature side to be maximum. The maximum temperature difference (ΔT max ) that each thermoelectric module can produce was measured. The maximum temperature difference (ΔT max ) was measured in a vacuum.

その結果、ｐ型及びｎ型熱電素子間にドライフィルムレジストが充填されている比較例の熱電モジュールは、最大温度差（ΔＴｍａｘ）が８８℃であったのに対し、ｐ型及びｎ型熱電素子間のドライフィルムレジストを除去した実施例の熱電モジュールは、最大温度差（ΔＴｍａｘ）が１００℃であった。ドライフィルム部の熱伝導率は０．０１３Ｗ／℃と極めて低いため、ｐ型及びｎ型熱電素子間にドライフィルムレジストが存在していると、基板間の熱の戻りにより、最大温度差（ΔＴｍａｘ）が１２℃程度低下した。 As a result, the thermoelectric module of the comparative example in which the dry film resist was filled between the p-type and n-type thermoelectric elements had a maximum temperature difference (ΔT max ) of 88 ° C., whereas the p-type and n-type thermoelectric modules The maximum temperature difference (ΔT max ) of the thermoelectric module of the example from which the dry film resist between elements was removed was 100 ° C. Since the thermal conductivity of the dry film portion is as extremely low as 0.013 W / ° C., if a dry film resist exists between the p-type and n-type thermoelectric elements, the maximum temperature difference (ΔT max ) decreased by about 12 ° C.

（ａ）本発明の第１の実施形態の熱電モジュールを示す斜視図であり、（ｂ）はその断面図である。(A) It is a perspective view which shows the thermoelectric module of the 1st Embodiment of this invention, (b) is the sectional drawing. 本発明の第１の実施形態の熱電モジュールの製造方法を示すフローチャート図である。It is a flowchart figure which shows the manufacturing method of the thermoelectric module of the 1st Embodiment of this invention. 本発明の第１の実施形態の熱電モジュールの製造方法を示す斜視図である。It is a perspective view which shows the manufacturing method of the thermoelectric module of the 1st Embodiment of this invention. 本発明の第１の実施形態の熱電モジュールの製造方法における図２の次の工程を示す斜視図である。It is a perspective view which shows the next process of FIG. 2 in the manufacturing method of the thermoelectric module of the 1st Embodiment of this invention. 本発明の第１の実施形態の熱電モジュールの製造方法における図３の次の工程を示す斜視図である。It is a perspective view which shows the next process of FIG. 3 in the manufacturing method of the thermoelectric module of the 1st Embodiment of this invention. 本発明の第１の実施形態の熱電モジュールの製造方法における図４の次の工程を示す斜視図である。It is a perspective view which shows the next process of FIG. 4 in the manufacturing method of the thermoelectric module of the 1st Embodiment of this invention. （ａ）本発明の第１の実施形態の熱電モジュールの製造方法における図５の次の工程を示す平面図であり、（ｂ）はその断面図である。(A) It is a top view which shows the next process of FIG. 5 in the manufacturing method of the thermoelectric module of the 1st Embodiment of this invention, (b) is the sectional drawing. （ａ）本発明の第１の実施形態の熱電モジュールの製造方法における図６（ａ）の次の工程を示す平面図であり、（ｂ）はその断面図である。(A) It is a top view which shows the next process of Fig.6 (a) in the manufacturing method of the thermoelectric module of the 1st Embodiment of this invention, (b) is the sectional drawing. （ａ）本発明の第１の実施形態の熱電モジュールの製造方法における図７（ａ）の次の工程を示す平面図であり、（ｂ）はその断面図である。(A) It is a top view which shows the next process of FIG. 7 (a) in the manufacturing method of the thermoelectric module of the 1st Embodiment of this invention, (b) is the sectional drawing. （ａ）本発明の第１の実施形態の熱電モジュールの製造方法における図８（ａ）の次の工程を示す平面図であり、（ｂ）はその断面図である。(A) It is a top view which shows the next process of Fig.8 (a) in the manufacturing method of the thermoelectric module of the 1st Embodiment of this invention, (b) is the sectional drawing. （ａ）本発明の第１の実施形態の熱電モジュールの製造方法における図９（ａ）の次の工程を示す平面図であり、（ｂ）はその断面図である。(A) It is a top view which shows the next process of Fig.9 (a) in the manufacturing method of the thermoelectric module of the 1st Embodiment of this invention, (b) is the sectional drawing. （ａ）本発明の第１の実施形態の熱電モジュールの製造方法における図１０（ａ）の次の工程を示す斜視図であり、（ｂ）はその断面図である。(A) It is a perspective view which shows the next process of Fig.10 (a) in the manufacturing method of the thermoelectric module of the 1st Embodiment of this invention, (b) is the sectional drawing. （ａ）本発明の第１の実施形態の熱電モジュールの製造方法における図１１（ａ）の次の工程を示す斜視図であり、（ｂ）はその断面図である。(A) It is a perspective view which shows the next process of Fig.11 (a) in the manufacturing method of the thermoelectric module of the 1st Embodiment of this invention, (b) is the sectional drawing. （ａ）本発明の第１の実施形態の熱電モジュールの変形例を示す斜視図であり、（ｂ）はその断面図である。(A) It is a perspective view which shows the modification of the thermoelectric module of the 1st Embodiment of this invention, (b) is the sectional drawing. 従来の熱電モジュールの製造方法の一例を示すフローチャート図である。It is a flowchart figure which shows an example of the manufacturing method of the conventional thermoelectric module. 特許文献１に記載の熱電素子集積体を示す斜視図である。1 is a perspective view showing a thermoelectric element integrated body described in Patent Document 1. FIG. 特許文献２に記載の熱電素子集積体を示す斜視図である。10 is a perspective view showing a thermoelectric element assembly described in Patent Document 2. FIG. 特許文献３に記載の熱電素子集積体を示す斜視図である。10 is a perspective view showing a thermoelectric element integrated body described in Patent Document 3. FIG. （ａ）乃至（ｄ）は特許文献４に記載の熱電素子の製造方法をその工程順に示す斜視図である。(A) thru | or (d) is a perspective view which shows the manufacturing method of the thermoelectric element of patent document 4 in the order of the process. （ａ）及び（ｂ）は特許文献５に記載の熱電モジュールの製造方法をその工程順に示す斜視図である。(A) And (b) is a perspective view which shows the manufacturing method of the thermoelectric module of patent document 5 in order of the process.

符号の説明Explanation of symbols

１；ｐ型熱電材料ウエハ １ａ、１１１、１１６、１２１；ｐ型熱電材料 １ｐ、１０２ｐ；ｐ型熱電素子 ２；ｎ型熱電材料ウエハ ２ｂ、１１２、１１５、１２２；ｎ型熱電材料 ２ｎ、１０２ｎ；ｎ型熱電素子 ３、１２７；スペーサ ４；熱電材料積層体 ４ａ；積層体ウエハ ５；熱電材料集積体 ５ａ；熱電素子集積体 ６；レジスト ７ａ；下部電極（金属膜） ７ｂ；上部電極（金属膜） ７ｃ、７ｄ；金属膜 ８；下側基板 ９；上側基板 １０、２０、１００；熱電モジュール １０１；インゴット １０２；熱電素子 １０３；セラミックス基板 １０４；Ｃｕ電極 １０５；Ｎｉめっき層 １０６；基板 １１３、１１７；絶縁材 １１８、１２３；断熱材 １２５；ｐ型熱電材料棒材 １２６；ｎ型熱電材料棒材   1; p-type thermoelectric material wafer 1a, 111, 116, 121; p-type thermoelectric material 1p, 102p; p-type thermoelectric element 2; n-type thermoelectric material wafer 2b, 112, 115, 122; n-type thermoelectric material 2n, 102n; n-type thermoelectric element 3, 127; spacer 4; thermoelectric material laminate 4a; laminate wafer 5; thermoelectric material assembly 5a; thermoelectric element assembly 6; resist 7a; lower electrode (metal film) 7b; 7c, 7d; Metal film 8; Lower substrate 9; Upper substrate 10, 20, 100; Thermoelectric module 101; Ingot 102; Thermoelectric element 103; Ceramic substrate 104; Cu electrode 105; Ni plating layer 106; Substrate 113, 117 Insulating material 118, 123; heat insulating material 125; p-type thermoelectric material rod 126; n-type thermoelectric material rod

Claims (5)

基板上の各下部電極上に夫々１対のｐ型熱電素子及びｎ型熱電素子が配置され、隣接する１対の下部電極に配置されたｐ型熱電素子及びｎ型熱電素子のうち隣接するｐ型熱電素子及びｎ型熱電素子が１個の上部電極に接合されている熱電モジュールの製造方法において、ｐ型熱電材料及びｎ型熱電材料を所定の間隔で切断してｐ型熱電材料及びｎ型熱電材料のウエハを得る工程と、前記ｐ型熱電材料のウエハと前記ｎ型熱電材料のウエハと交互に配置しそれらの間にアルカリ性溶剤に可溶な熱硬化性樹脂シートからなる第１のスペーサを挿入して相互に接合して熱電材料積層体を得る工程と、この熱電材料積層体を所定の間隔で積層方向に切断して長尺のｐ型熱電材料及びｎ型熱電材料が夫々前記第１のスペーサを介して積層した積層部材を得る工程と、切断後の各積層部材を隣接する積層部材間でｐ型熱電材料とｎ型熱電材料とが対向するように１枚おきに切断面における面内方向に１８０°回転させて配置しそれらの間にアルカリ性溶剤に可溶な熱硬化性樹脂シートからなる第２のスペーサを挿入して相互に接合して一体化する工程と、この一体化した部材を所定の間隔で前記ｐ型熱電材料及びｎ型熱電材料の長手方向に直交する方向に切断して熱電素子集積体を得る工程と、この熱電素子集積体の下面を構成する熱電素子集積体の一方の切断面上に、隣接する１対のｐ型熱電材料及びｎ型熱電材料毎に１個となるように、下部電極を形成すると共に、隣接する下部電極のうち一方の下部電極に接触するｐ型熱電素子と他方の下部電極に接触するｎ型熱電素子とが１個の上部電極により接続されるようにして、前記熱電素子集積体の上面を構成する熱電素子集積体の他方の切断面上に複数個の上部電極を形成する工程と、前記熱電素子集積体と下部基板とを前記下部電極を介して接合する工程と、前記第１及び第２のスペーサをアルカリ性溶剤により溶解させて除去する工程と、を有することを特徴とする熱電モジュールの製造方法。 A pair of p-type thermoelectric elements and n-type thermoelectric elements are disposed on each lower electrode on the substrate, and adjacent p-type thermoelectric elements and n-type thermoelectric elements disposed on a pair of adjacent lower electrodes. In a method for manufacturing a thermoelectric module in which a p-type thermoelectric element and an n-type thermoelectric element are joined to one upper electrode, the p-type thermoelectric material and the n-type thermoelectric material are cut at a predetermined interval to obtain a p-type thermoelectric material and an n-type A step of obtaining a thermoelectric material wafer, and a first spacer comprising a thermosetting resin sheet which is alternately disposed between the p-type thermoelectric material wafer and the n-type thermoelectric material wafer and is soluble in an alkaline solvent therebetween. A thermoelectric material laminate obtained by inserting the thermoelectric material laminate and cutting the thermoelectric material laminate in the laminating direction at a predetermined interval so that the long p-type thermoelectric material and n-type thermoelectric material are A laminated member laminated through one spacer And every other laminated member after cutting is rotated 180 ° in the in-plane direction on the cut surface so that the p-type thermoelectric material and the n-type thermoelectric material face each other between adjacent laminated members. A step of inserting a second spacer made of a thermosetting resin sheet soluble in an alkaline solvent between them and joining them together and integrating the integrated member at a predetermined interval with the p-type thermoelectric Cutting the material and the n-type thermoelectric material in a direction orthogonal to the longitudinal direction to obtain a thermoelectric element assembly, and adjacent one cut surface of the thermoelectric element assembly constituting the lower surface of the thermoelectric element assembly A lower electrode is formed so that there is one for each pair of p-type thermoelectric material and n-type thermoelectric material, and a p-type thermoelectric element that contacts one of the adjacent lower electrodes and the other lower electrode N-type thermoelectric element in contact with the upper electrode Forming a plurality of upper electrodes on the other cut surface of the thermoelectric element assembly constituting the upper surface of the thermoelectric element assembly, and connecting the thermoelectric element assembly and the lower substrate. A method of manufacturing a thermoelectric module, comprising: a step of bonding via the lower electrode; and a step of dissolving and removing the first and second spacers with an alkaline solvent . 基板上の各下部電極上に夫々１対のｐ型熱電素子及びｎ型熱電素子が配置され、隣接する１対の下部電極に配置されたｐ型熱電素子及びｎ型熱電素子のうち隣接するｐ型熱電素子及びｎ型熱電素子が１個の上部電極に接合されている熱電モジュールの製造方法において、ｐ型熱電材料及びｎ型熱電材料を所定の間隔で切断してｐ型熱電材料及びｎ型熱電材料のウエハを得る工程と、前記ｐ型熱電材料のウエハと前記ｎ型熱電材料のウエハと交互に配置しそれらの間にアルカリ性溶剤に可溶な熱硬化性樹脂シートからなる第１のスペーサを挿入して相互に接合して熱電材料積層体を得る工程と、この熱電材料積層体を所定の間隔で積層方向に切断して長尺のｐ型熱電材料及びｎ型熱電材料が夫々前記第１のスペーサを介して積層した積層部材を得る工程と、切断後の各積層部材を隣接する積層部材間でｐ型熱電材料とｎ型熱電材料とが対向するように１枚おきに切断面における面内方向に１８０°回転させて配置しそれらの間にアルカリ性溶剤に可溶な熱硬化性樹脂シートからなる第２のスペーサを挿入して相互に接合して一体化する工程と、この一体化した部材を所定の間隔で前記ｐ型熱電材料及びｎ型熱電材料の長手方向に直交する方向に切断して熱電素子集積体を得る工程と、この熱電素子集積体の下面を構成する熱電素子集積体の一方の切断面上に、隣接する１対のｐ型熱電材料及びｎ型熱電材料毎に１個となるように、下部電極を形成すると共に、隣接する下部電極のうち一方の下部電極に接触するｐ型熱電素子と他方の下部電極に接触するｎ型熱電素子とが１個の上部電極により接続されるようにして、前記熱電素子集積体の上面を構成する熱電素子集積体の他方の切断面上に複数個の上部電極を形成する工程と、前記熱電素子集積体と下部基板及び上部基板とを前記下部電極及び上部電極を介して接合する工程と、前記第１及び第２のスペーサをアルカリ性溶剤により溶解させて除去する工程と、を有することを特徴とする熱電モジュールの製造方法。 A pair of p-type thermoelectric elements and n-type thermoelectric elements are disposed on each lower electrode on the substrate, and adjacent p-type thermoelectric elements and n-type thermoelectric elements disposed on a pair of adjacent lower electrodes. In a method for manufacturing a thermoelectric module in which a p-type thermoelectric element and an n-type thermoelectric element are joined to one upper electrode, the p-type thermoelectric material and the n-type thermoelectric material are cut at a predetermined interval to obtain a p-type thermoelectric material and an n-type A step of obtaining a thermoelectric material wafer, and a first spacer comprising a thermosetting resin sheet which is alternately disposed between the p-type thermoelectric material wafer and the n-type thermoelectric material wafer and is soluble in an alkaline solvent therebetween. A thermoelectric material laminate obtained by inserting the thermoelectric material laminate and cutting the thermoelectric material laminate in the laminating direction at a predetermined interval so that the long p-type thermoelectric material and n-type thermoelectric material are A laminated member laminated through one spacer And every other laminated member after cutting is rotated 180 ° in the in-plane direction on the cut surface so that the p-type thermoelectric material and the n-type thermoelectric material face each other between adjacent laminated members. A step of inserting a second spacer made of a thermosetting resin sheet soluble in an alkaline solvent between them and joining them together and integrating the integrated member at a predetermined interval with the p-type thermoelectric Cutting the material and the n-type thermoelectric material in a direction orthogonal to the longitudinal direction to obtain a thermoelectric element assembly, and adjacent one cut surface of the thermoelectric element assembly constituting the lower surface of the thermoelectric element assembly A lower electrode is formed so that there is one for each pair of p-type thermoelectric material and n-type thermoelectric material, and a p-type thermoelectric element that contacts one of the adjacent lower electrodes and the other lower electrode N-type thermoelectric element in contact with the upper electrode So as to be connected by a step of forming a plurality of upper electrodes on the other cut surface of the thermoelectric element stack which constitutes the upper surface of the thermoelectric element stack, the thermoelectric element stack and the lower substrate and the upper A method of manufacturing a thermoelectric module, comprising: a step of bonding a substrate through the lower electrode and the upper electrode; and a step of dissolving and removing the first and second spacers with an alkaline solvent. . 前記ｐ型熱電材料のウエハ及び前記ｎ型熱電材料のウエハに前記第１のスペーサを積層し接合することを特徴とする請求項１又は２に記載の熱電モジュールの製造方法。 The method of manufacturing a thermoelectric module according to claim 1, wherein the first spacer is stacked and bonded to the p-type thermoelectric material wafer and the n-type thermoelectric material wafer. 前記切断後の各積層部材に前記第２のスペーサを積層し接合することを特徴とする請求項１乃至３のいずれか１項に記載の熱電モジュールの製造方法。 4. The method of manufacturing a thermoelectric module according to claim 1, wherein the second spacer is laminated and bonded to each of the cut laminated members. 5. 前記第１及び第２のスペーサは、ドライフィルムレジストであることを特徴とする請求項１乃至４のいずれか１項に記載の熱電モジュールの製造方法。 The method of manufacturing a thermoelectric module according to claim 1, wherein the first and second spacers are dry film resists.
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