TW202105777A - Method for forming solder receiving layer on chip of thermoelectric conversion material - Google Patents

Abstract

In order to provide a method for forming a solder receiving layer on a chip of a thermoelectric conversion material that can suppress reduction in thermoelectric performance, this method, for forming a solder receiving layer on a chip that has a top surface, a bottom surface and a side surface and that is of a thermoelectric conversion material comprising a thermoelectric semiconductor composition, involves (A) a step for forming a solder receiving layer on all surfaces of a thermoelectric conversion material chip, and (B) a step for removing all or part of the solder receiving layer formed on the side surface of the thermoelectric conversion material chip obtained in step (A).

Description

對熱電轉換材料的晶片的焊錫受理層的形成方法Method for forming solder receiving layer for wafer of thermoelectric conversion material

本發明關於進行熱與電力的相互能量轉換之對熱電轉換材料的晶片的焊錫受理層的形成方法。The present invention relates to a method for forming a solder receiving layer for a wafer of thermoelectric conversion material that performs mutual energy conversion between heat and electricity.

自以往以來，作為能量的有效利用手段之一，有藉由席貝克(Seebeck)效應或帕耳帖(Peltier)效應等熱電效應之熱電轉換模組，將熱能與電能直接相互轉換之裝置。 作為前述熱電轉換模組，已知使用所謂π型的熱電轉換元件。π型係將互相分離的一對電極設於基板上，例如於一個電極之上設置P型熱電元件，於另一個電極之上同樣地互相分離地設置N型熱電元件，使兩個熱電材料之上表面連接至對向的基板之電極而構成。 近年來，要求熱電轉換模組的彎曲性提升、薄型化及熱電性能之提升等。為了滿足此等之要求，例如作為用於熱電轉換模組的基板，從耐熱性及彎曲性之觀點來看，使用聚醯亞胺等之樹脂基板。又，N型的熱電半導體材料、P型的熱電半導體材料係使用樹脂等作為黏結劑，從熱電性能之觀點來看，鉍碲化物系材料係在作為前述電極，有使用熱傳導率高、低電阻的Cu電極(專利文獻1、2等)。 於如此的構成中，例如在300℃等之高溫度下退火處理熱電轉換模組之步驟中，於熱電轉換材料中所含有熱電半導體材料與Cu電極之接合部中，因擴散而形成合金層，結果在電極發生破裂或剝落，熱電轉換材料與Cu電極間的電阻值會增大，熱電性能會降低(專利文獻3等)。 為了消除上述，於熱電轉換模組之製造中，有以單片使用事先經退火處理之熱電轉換材料的晶片之情況。此時，於熱電轉換材料的晶片上與電極之接合中，通常會使用焊錫材料層，但例如如同用於熱電轉換材料的鉍碲化物系材料，有與焊錫材料層的密著性差，為了改善其，有將焊錫受理層層合於熱電轉換材料的晶片之面。 先前技術文獻 專利文獻Since the past, as one of the effective utilization methods of energy, there has been a thermoelectric conversion module that directly converts heat energy and electrical energy through thermoelectric effects such as the Seebeck effect or the Peltier effect. As the aforementioned thermoelectric conversion module, it is known to use a so-called π-type thermoelectric conversion element. In the π type system, a pair of separated electrodes is provided on the substrate. For example, a P-type thermoelectric element is provided on one electrode, and an N-type thermoelectric element is also separated from each other on the other electrode, so that the two thermoelectric materials are separated from each other. The upper surface is connected to the electrode of the opposite substrate. In recent years, improvement in flexibility, thinning, and improvement in thermoelectric performance of thermoelectric conversion modules have been required. In order to meet these requirements, for example, as a substrate for a thermoelectric conversion module, a resin substrate such as polyimide is used from the viewpoint of heat resistance and flexibility. In addition, N-type thermoelectric semiconductor materials and P-type thermoelectric semiconductor materials use resins as binders. From the standpoint of thermoelectric performance, bismuth telluride-based materials are used as the aforementioned electrodes, which have high thermal conductivity and low electrical resistance. Cu electrodes (Patent Documents 1, 2, etc.). In such a configuration, for example, in the step of annealing the thermoelectric conversion module at a high temperature such as 300°C, an alloy layer is formed due to diffusion in the junction between the thermoelectric semiconductor material contained in the thermoelectric conversion material and the Cu electrode. As a result, cracking or peeling of the electrode occurs, the resistance value between the thermoelectric conversion material and the Cu electrode increases, and the thermoelectric performance decreases (Patent Document 3, etc.). In order to eliminate the above, in the manufacture of thermoelectric conversion modules, there is a case of using a single chip of a thermoelectric conversion material that has been annealed in advance. At this time, a solder material layer is usually used in the bonding between the thermoelectric conversion material wafer and the electrode. However, for example, the bismuth telluride-based material used for the thermoelectric conversion material has poor adhesion to the solder material layer. In order to improve There is a surface where a solder receiving layer is laminated on a wafer of thermoelectric conversion material. Prior art literature Patent literature

專利文獻1：日本特開2010-192764號公報 專利文獻2：日本特開2012-204452號公報 專利文獻3：國際公開第2018/168837號Patent Document 1: Japanese Patent Application Publication No. 2010-192764 Patent Document 2: Japanese Patent Application Publication No. 2012-204452 Patent Document 3: International Publication No. 2018/168837

發明所欲解決的課題The problem to be solved by the invention

然而，根據本發明者們之檢討，發現：將焊錫受理層層合於熱電轉換材料的晶片的全部的面時，在與熱電轉換材料的晶片之接合有關的上下表面以外的側面，亦層合有焊錫受理層，因此在熱電轉換材料的晶片之上下表面間的熱電半導體組成物中流動的電流變少，許多的電流會在焊錫受理層中流動，無法展現熱電轉換材料的晶片本來具有的熱電性能，結果有發生熱電性能降低等新的問題之掛慮。 又，同樣地，根據本發明者們之檢討，發現：即使為以印刷法等僅在熱電轉換材料的晶片之上下表面層合的焊錫受理層，也熱電轉換材料的晶片之上表面或下表面與焊錫受理層各自的界面之接觸電阻係增大，亦有發生熱電性能降低等新的問題之掛慮。However, according to the review of the present inventors, it was found that when the solder receiving layer is laminated on the entire surface of the thermoelectric conversion material wafer, the side surfaces other than the upper and lower surfaces related to the bonding of the thermoelectric conversion material wafer are also laminated There is a solder receiving layer, so the current flowing in the thermoelectric semiconductor composition between the upper and lower surfaces of the thermoelectric conversion material wafer is reduced, and a lot of current flows in the solder receiving layer, and the original thermoelectricity of the thermoelectric conversion material wafer cannot be displayed. As a result, there are concerns about new problems such as degradation of thermoelectric performance. Also, similarly, according to the review of the present inventors, it was found that even if it is a solder receiving layer laminated only on the upper and lower surfaces of the wafer of thermoelectric conversion material by a printing method, the upper or lower surface of the wafer of thermoelectric conversion material The contact resistance of the respective interface with the solder receiving layer increases, and there are concerns about new problems such as degradation of thermoelectric performance.

本發明係鑒於上述，課題在於提供能抑制熱電性能的降低之對熱電轉換材料的晶片的焊錫受理層的形成方法。 解決課題的手段In view of the foregoing, the present invention has a problem to provide a method for forming a solder receiving layer for a wafer of a thermoelectric conversion material that can suppress a decrease in thermoelectric performance. Means to solve the problem

本發明者們為了解決上述課題而重複專心致力的檢討，結果發現：將焊錫受理層形成於具有上表面、下表面及側面的熱電轉換材料的晶片上後，藉由從該熱電轉換材料的晶片之至少側面，去除所形成的焊錫受理層之形成方法，而減少熱電轉換材料的晶片之上下表面間的導通性，展現熱電轉換材料的晶片本來具有之熱電性能，而完成本發明。 即，本發明提供以下之(1)～(9)。 (1)一種焊錫受理層的形成方法，其係將焊錫受理層形成於具有上表面、下表面及側面的熱電轉換材料的晶片上之方法，前述熱電轉換材料係包含熱電半導體組成物而成，包含下述步驟(A)及步驟(B)： (A)將前述焊錫受理層形成於前述熱電轉換材料的晶片的全部的面上之步驟； (B)將以前述(A)之步驟而得到的形成於前述熱電轉換材料的晶片的側面上的焊錫受理層之全部或一部分予以去除之步驟。 (2)如上述(1)記載之焊錫受理層的形成方法，其中，以無電電鍍法、電鍍法或真空成膜法來進行前述焊錫受理層的形成。 (3)如上述(1)或(2)記載之焊錫受理層的形成方法，其中，以機械拋光法、化學拋光法及電解拋光法的表面拋光法中的至少1種來進行前述焊錫受理層的去除。 (4)如上述(1)～(3)中任一項記載之焊錫受理層的形成方法，其中，前述熱電轉換材料的晶片的厚度為100nm～1000 μm。 (5)如上述(1)～(4)中任一項記載之焊錫受理層的形成方法，其中，前述熱電半導體組成物包含熱電半導體材料，且該熱電半導體材料為鉍-碲系熱電半導體材料、碲化物系熱電半導體材料、銻-碲系熱電半導體材料或鉍硒化物系熱電半導體材料。 (6)如上述(1)～(5)中任一項記載之焊錫受理層的形成方法，其中，前述熱電半導體組成物更包含耐熱性樹脂。 (7)如上述(1)～(6)中任一項記載之焊錫受理層的形成方法，其中，前述耐熱性樹脂為聚醯亞胺樹脂、聚醯胺樹脂、聚醯胺醯亞胺樹脂或環氧樹脂。 (8)如上述(1)～(7)中任一項記載之焊錫受理層的形成方法，其中，前述熱電半導體組成物更包含離子液體及/或無機離子性化合物。 (9)一種熱電轉換模組的製造方法，其係使用複數個藉由上述(1)～(8)中任一項記載之焊錫受理層的形成方法而得到的具有焊錫受理層的前述熱電轉換材料的晶片的熱電轉換模組的製造方法，包含下述步驟(xi)至步驟(xvi)：(xi)將第一電極形成於第一樹脂薄膜上之步驟；(xii)將第二電極形成於第二樹脂薄膜上之步驟；(xiii)將焊錫材料層形成於以前述(xi)之步驟而得到的前述第一電極上之步驟；(xiv)將前述熱電轉換材料的晶片的具有焊錫受理層的一面載置於以前述(xiii)之步驟而得到的前述焊錫材料層上之步驟；(xv)將以前述(xiv)之步驟而載置的前述熱電轉換材料的晶片的具有焊錫受理層的一面，隔著以前述(xiii)之步驟而得到的前述焊錫材料層，來與前述第一電極進行接合之步驟；(xvi)將前述(xv)之步驟後的前述熱電轉換材料的晶片的另一面的焊錫受理層，與以前述(xii)之步驟而得到的前述第二電極，以隔著焊錫材料層來進行接合之步驟。 發明的效果In order to solve the above-mentioned problems, the inventors have repeated intensive and dedicated examinations. As a result, they have found that after forming a solder receiving layer on a wafer with a thermoelectric conversion material on the upper surface, lower surface, and side surfaces, At least on the side surface, the method of forming the solder receiving layer is removed to reduce the conductivity between the upper and lower surfaces of the thermoelectric conversion material wafer, and exhibit the original thermoelectric performance of the thermoelectric conversion material wafer, thus completing the present invention. That is, the present invention provides the following (1) to (9). (1) A method for forming a solder receiving layer, which is a method of forming a solder receiving layer on a wafer having a thermoelectric conversion material having an upper surface, a lower surface and a side surface, wherein the thermoelectric conversion material contains a thermoelectric semiconductor composition, Including the following steps (A) and (B): (A) A step of forming the solder receiving layer on the entire surface of the wafer of the thermoelectric conversion material; (B) A step of removing all or part of the solder receiving layer formed on the side surface of the wafer of the thermoelectric conversion material obtained in the step (A). (2) The method for forming a solder receiving layer as described in (1) above, wherein the solder receiving layer is formed by an electroless plating method, an electroplating method, or a vacuum film forming method. (3) The method for forming a solder receiving layer as described in (1) or (2) above, wherein the solder receiving layer is formed by at least one of surface polishing methods of mechanical polishing, chemical polishing, and electrolytic polishing Removal. (4) The method for forming a solder receiving layer according to any one of (1) to (3) above, wherein the thickness of the wafer of the thermoelectric conversion material is 100 nm to 1000 μm. (5) The method for forming a solder receiving layer according to any one of (1) to (4) above, wherein the thermoelectric semiconductor composition includes a thermoelectric semiconductor material, and the thermoelectric semiconductor material is a bismuth-tellurium based thermoelectric semiconductor material , Telluride-based thermoelectric semiconductor materials, antimony-tellurium-based thermoelectric semiconductor materials, or bismuth selenide-based thermoelectric semiconductor materials. (6) The method for forming a solder receiving layer according to any one of (1) to (5) above, wherein the thermoelectric semiconductor composition further contains a heat-resistant resin. (7) The method for forming a solder receiving layer as described in any one of (1) to (6) above, wherein the heat-resistant resin is a polyimide resin, a polyimide resin, or a polyimide resin Or epoxy. (8) The method for forming a solder receiving layer according to any one of (1) to (7) above, wherein the thermoelectric semiconductor composition further contains an ionic liquid and/or an inorganic ionic compound. (9) A method of manufacturing a thermoelectric conversion module using a plurality of the aforementioned thermoelectric conversions having a solder receiving layer obtained by the method for forming a solder receiving layer described in any one of (1) to (8) above The method for manufacturing a thermoelectric conversion module of a wafer of material includes the following steps (xi) to step (xvi): (xi) a step of forming a first electrode on a first resin film; (xii) forming a second electrode The step on the second resin film; (xiii) the step of forming a solder material layer on the first electrode obtained in the step (xi); (xiv) accepting the solder of the wafer with the thermoelectric conversion material The step of placing one side of the layer on the solder material layer obtained in the step (xiii); (xv) the wafer of the thermoelectric conversion material placed in the step (xiv) has a solder receiving layer The step of bonding with the first electrode via the solder material layer obtained in the step (xiii) above; (xvi) the step of joining the wafer of the thermoelectric conversion material after the step (xv) The step of joining the solder receiving layer on the other side to the second electrode obtained in the step (xii) above via a layer of solder material. The effect of the invention

依照本發明，可提供能抑制熱電性能的降低之對熱電轉換材料的晶片的焊錫受理層的形成方法。According to the present invention, it is possible to provide a method of forming a solder receiving layer for a wafer of a thermoelectric conversion material that can suppress a decrease in thermoelectric performance.

實施發明的形態Implementation of the invention

[對熱電轉換材料的晶片的焊錫受理層的形成方法] 本發明之對熱電轉換材料的晶片的焊錫受理層的形成方法係將焊錫受理層形成於具有上表面、下表面及側面的熱電轉換材料的晶片上之方法，前述熱電轉換材料係包含熱電半導體組成物而成，其特徵為包含：(A)將前述焊錫受理層形成於前述熱電轉換材料的晶片的全部的面上之步驟，及(B)將以前述(A)之步驟而得到的形成於前述熱電轉換材料的晶片的側面上的焊錫受理層之全部或一部分予以去除之步驟。 於本發明之對熱電轉換材料的晶片的焊錫受理層的形成方法中，在具有上表面、下表面及側面的包含熱電半導體組成物而成之熱電轉換材料的晶片的全部的面上形成焊錫受理層後，於所得的焊錫受理層之中，藉由將形成於熱電轉換材料的晶片的側面上的焊錫受理層予以全部去除或一部分去除，而形成焊錫受理層。 此處，所謂「將形成於晶片的側面上的焊錫受理層之一部分予以去除」，就是意指因在熱電轉換材料的晶片之上下表面間焊錫受理層之存在，而在熱電轉換材料中流動的電流變少，為了不使許多的電流在焊錫受理層中流動，將熱電轉換材料的晶片的側面之高度方向的焊錫受理層之一部分在側面之全周圍中連續地去除。 又，作為一個態樣，從製造的容易度及良率之觀點來看，較佳為於所得的焊錫受理層之中，藉由同時去除熱電轉換材料的晶片的側面之焊錫受理層的全部及從熱電轉換材料的晶片的側面之壁起的深度方向之一部分，而僅在熱電轉換材料的晶片上表面及下表面形成焊錫受理層。 上述形成方法所得之具有焊錫受理層的熱電轉換材料的晶片，係在熱電轉換材料的晶片之與電極的接合有關的至少上下表面，形成焊錫受理層，在晶片的側面，不形成焊錫受理層，但即使形成也由於以熱電轉換材料的晶片之上下表面間不通過側面的焊錫受理層而電導通之方式而形成，包含將與焊錫受理層的界面之接觸電阻值抑制在低，將具有該焊錫受理層之熱電轉換材料的晶片應用於熱電轉換模組時，不發生熱電性能降低等之問題。 再者，於本說明書中，「具有上表面、下表面及側面之包含熱電半導體組成物而成之熱電轉換材料的晶片」中的「具有上表面、下表面及側面」，係意指熱電轉換材料的晶片之形狀，只要在各面之各自上能形成焊錫受理層，則沒有特別的限制，但作為熱電轉換材料的晶片之形狀，從包含與電極的接合性之形狀安定性的觀點來看，可舉出角柱狀、圓柱狀、圓錐台狀、角錐台狀等。作為角柱狀，可舉出三角柱狀、長方體狀、立方體狀、五角柱狀、六角柱狀等。其中，從焊錫受理層的去除容易度、與電極的接合性、熱電轉換材料的晶片之形成及熱電性能之觀點來看，熱電轉換材料的晶片之形狀較佳為長方體狀、立方體狀或圓柱狀，更佳為長方體狀、立方體狀。[Formation method of solder receiving layer on wafer of thermoelectric conversion material] The method for forming a solder receiving layer of a wafer of thermoelectric conversion material of the present invention is a method of forming a solder receiving layer on a wafer of thermoelectric conversion material having an upper surface, a lower surface, and a side surface. The thermoelectric conversion material includes a thermoelectric semiconductor composition. It is characterized by including: (A) the step of forming the solder receiving layer on the entire surface of the wafer of the thermoelectric conversion material, and (B) the step of (A) on the The step of removing all or part of the solder receiving layer on the side surface of the wafer of the thermoelectric conversion material. In the method of forming a solder receiving layer for a thermoelectric conversion material wafer of the present invention, the solder receiving layer is formed on all the surfaces of the thermoelectric conversion material wafer including the thermoelectric semiconductor composition having an upper surface, a lower surface, and a side surface. After layering, among the obtained solder receiving layer, the solder receiving layer formed on the side surface of the thermoelectric conversion material wafer is completely removed or partly removed to form the solder receiving layer. Here, the phrase "removing part of the solder receiving layer formed on the side surface of the wafer" means that the solder receiving layer between the upper and lower surfaces of the thermoelectric conversion material flows in the thermoelectric conversion material due to the existence of the solder receiving layer between the upper and lower surfaces of the wafer. In order to prevent a large amount of current from flowing in the solder receiving layer, the current is reduced, and a part of the solder receiving layer in the height direction of the side surface of the thermoelectric conversion material wafer is continuously removed over the entire circumference of the side surface. In addition, as one aspect, from the viewpoints of ease of manufacture and yield, it is preferable to simultaneously remove all of the solder receiving layer on the side surface of the wafer of the thermoelectric conversion material in the obtained solder receiving layer and A portion in the depth direction from the side wall of the thermoelectric conversion material wafer, and the solder receiving layer is formed only on the upper surface and the lower surface of the thermoelectric conversion material wafer. The thermoelectric conversion material wafer with the solder receiving layer obtained by the above forming method is formed on at least the upper and lower surfaces of the thermoelectric conversion material wafer related to the bonding of the electrodes, and the solder receiving layer is formed, and the solder receiving layer is not formed on the side surface of the wafer. However, even if it is formed, it is formed in a way that the upper and lower surfaces of the wafer of thermoelectric conversion material do not pass through the solder receiving layer on the side surface, and the contact resistance value of the interface with the solder receiving layer is suppressed to be low. When the wafer of the thermoelectric conversion material of the receiving layer is applied to the thermoelectric conversion module, there will be no problems such as degradation of thermoelectric performance. Furthermore, in this specification, "a wafer containing a thermoelectric conversion material made of a thermoelectric semiconductor composition with an upper surface, a lower surface, and a side surface" refers to the term "having an upper surface, a lower surface, and a side surface". The shape of the material of the wafer is not particularly limited as long as the solder receiving layer can be formed on each surface. However, the shape of the wafer as a thermoelectric conversion material is from the viewpoint of shape stability including the bondability with the electrode , For example, prismatic shape, cylindrical shape, truncated cone shape, and truncated cone shape. Examples of the angular column shape include a triangular column shape, a rectangular parallelepiped shape, a cube shape, a pentagonal column shape, and a hexagonal column shape. Among them, from the viewpoints of ease of removal of the solder receiving layer, bonding with electrodes, formation of the thermoelectric conversion material wafer, and thermoelectric performance, the shape of the thermoelectric conversion material wafer is preferably rectangular, cubic, or cylindrical. , More preferably a rectangular parallelepiped shape or a cube shape.

圖1係用於說明本發明之對熱電轉換材料的晶片的焊錫受理層的形成方法之實施態樣的一例之剖面構成圖，(a)為在熱電轉換材料的晶片之上表面、下表面及側面的全部的面上形成焊錫受理層後之剖面圖，顯示於包含P型的熱電半導體材料之P型熱電轉換材料的晶片1p及包含N型的熱電半導體材料之N型熱電轉換材料的晶片1n之各自的上表面2a、下表面2b及側面2c的全部的面上形成有焊錫受理層3之態樣，(b)為從熱電轉換材料的晶片的側面去除焊錫受理層後之剖面圖，藉由去除在熱電轉換材料的晶片1p及N型熱電轉換材料的晶片1n之各自的側面2c上所形成的焊錫受理層3，而形成僅在P型熱電轉換材料的晶片1p及N型熱電轉換材料的晶片1n之各自的上表面2a及下表面2b具有焊錫受理層3的P型熱電轉換材料的晶片4p及N型熱電轉換材料的晶片4n。1 is a cross-sectional configuration diagram for explaining an example of the implementation of the method of forming the solder receiving layer of the thermoelectric conversion material wafer of the present invention, (a) is the upper surface, the lower surface and the lower surface of the thermoelectric conversion material wafer The cross-sectional view after the solder receiving layer is formed on all the sides of the side surface is shown on a P-type thermoelectric conversion material wafer 1p containing a P-type thermoelectric semiconductor material and an N-type thermoelectric conversion material wafer 1n containing an N-type thermoelectric semiconductor material Each of the upper surface 2a, lower surface 2b, and side surface 2c has a solder receiving layer 3 formed on all of the surfaces. (b) is a cross-sectional view after removing the solder receiving layer from the side surface of the thermoelectric conversion material wafer. The solder receiving layer 3 formed on each side surface 2c of the wafer 1p of thermoelectric conversion material and the wafer 1n of N type thermoelectric conversion material is removed, and the wafer 1p of the P type thermoelectric conversion material and the N type thermoelectric conversion material are formed only Each of the upper surface 2a and the lower surface 2b of the wafer 1n has a P-type thermoelectric conversion material wafer 4p and an N-type thermoelectric conversion material wafer 4n of the solder receiving layer 3.

於本發明之焊錫受理層的形成方法中，包含焊錫受理層形成步驟及焊錫受理層去除步驟。The method for forming a solder receiving layer of the present invention includes a solder receiving layer forming step and a solder receiving layer removal step.

(A)焊錫受理層形成步驟 焊錫受理層形成步驟係在熱電轉換材料的晶片之上表面、下表面及側面的全部的面上形成焊錫受理層之步驟，如前述，例如於圖1(a)中，在包含P型的熱電半導體材料之P型熱電轉換材料的晶片1p之上表面2a、下表面2b及側面2c的全部的面上形成焊錫受理層3之步驟。 焊錫受理層係可提高熱電轉換材料的晶片與電極上的焊錫材料層之接合強度。(A) Steps for forming solder receiving layer The step of forming a solder receiving layer is a step of forming a solder receiving layer on all the upper, lower, and side surfaces of the thermoelectric conversion material wafer. As described above, for example, in Figure 1(a), the P-type thermoelectric The step of forming the solder receiving layer 3 on all of the upper surface 2a, the lower surface 2b, and the side surface 2c of the wafer 1p of the P-type thermoelectric conversion material of semiconductor material. The solder receiving layer can improve the bonding strength between the thermoelectric conversion material wafer and the solder material layer on the electrode.

(焊錫受理層的形成方法) 作為焊錫受理層的形成方法，並沒有特別的限制，可舉出鍍敷法、銀鹽法、金屬箔之層合、或真空蒸鍍法、濺鍍法、離子鍍法等之PVD(物理氣相成長法)、或熱CVD、原子層蒸鍍(ALD)等之CVD(化學氣相成長法)等之真空成膜法等，更且浸塗法、旋塗法、噴塗法、凹版塗佈法、模塗法、刮刀法等之各種塗佈法，可按照焊錫受理層的材料而適宜選擇。(Method of forming solder receiving layer) The method of forming the solder receiving layer is not particularly limited. Examples include plating method, silver salt method, metal foil lamination, or vacuum evaporation method, sputtering method, ion plating method and other PVD (physical vapor deposition method). Phase growth method), or CVD (chemical vapor growth method) such as thermal CVD, atomic layer deposition (ALD) and other vacuum film forming methods, etc., and also dip coating method, spin coating method, spraying method, gravure coating Various coating methods such as method, die coating method, doctor blade method, etc. can be appropriately selected according to the material of the solder receiving layer.

焊錫受理層較佳為包含金屬材料。金屬材料較佳為由金、銀、銠、鉑、鉻、鈀、錫、鎳及包含此等的任一金屬材料之合金所選出的至少1種。其中，更佳為金、銀、鎳、或錫及金、鎳及金之2層構成，從材料成本、高熱傳導性、接合安定性之觀點來看，更佳為銀。 於焊錫受理層，從維持熱電性能之觀點來看，要求高的導電性、高的熱傳導性，且從能減小與熱電轉換材料的晶片之界面的接觸電阻之觀點來看，較佳為使用以鍍敷法或真空成膜法所成膜的焊錫受理層。 其中，從設備費用、維持、生產性、材料成本等之觀點來看，更佳為以鍍敷法進行。 鍍敷法亦可為乾式鍍敷法，但較佳為能容易地調整厚度之濕式鍍敷法。作為濕式鍍敷法，較佳為電鍍法、無電電鍍法。 焊錫受理層的厚度較佳為10nm～50μm，更佳為50nm～16μm，尤佳為200nm～4μm，特佳為500nm～3μm。若焊錫受理層的厚度在該範圍，則與包含樹脂之熱電轉換材料的晶片之面的密著性及與電極側的焊錫材料層之面的密著性優異，得到與電極的可靠性高之接合。又，導電性係自不待言，由於可維持高的熱傳導性，結果作為熱電轉換模組的熱電性能不降低而可被維持。The solder receiving layer preferably contains a metal material. The metal material is preferably at least one selected from gold, silver, rhodium, platinum, chromium, palladium, tin, nickel, and alloys containing any of these metal materials. Among them, a two-layer structure of gold, silver, nickel, or tin and gold, nickel and gold is more preferable, and from the viewpoint of material cost, high thermal conductivity, and bonding stability, silver is more preferable. For the solder receiving layer, from the viewpoint of maintaining thermoelectric performance, high electrical conductivity and high thermal conductivity are required, and from the viewpoint of reducing the contact resistance of the interface with the thermoelectric conversion material chip, it is preferable to use Solder receiving layer formed by plating method or vacuum film forming method. Among them, from the viewpoint of equipment cost, maintenance, productivity, material cost, etc., the plating method is more preferable. The plating method may be a dry plating method, but a wet plating method in which the thickness can be easily adjusted is preferred. As the wet plating method, an electroplating method or an electroless plating method is preferable. The thickness of the solder receiving layer is preferably 10 nm to 50 μm, more preferably 50 nm to 16 μm, particularly preferably 200 nm to 4 μm, particularly preferably 500 nm to 3 μm. If the thickness of the solder receiving layer is within this range, the adhesion to the surface of the wafer containing the resin thermoelectric conversion material and the adhesion to the surface of the solder material layer on the electrode side are excellent, and the reliability of the electrode is high. Join. In addition, it goes without saying that the conductivity is high, and high thermal conductivity can be maintained. As a result, the thermoelectric performance as a thermoelectric conversion module can be maintained without degrading.

(B)焊錫受理層去除步驟 焊錫受理層去除步驟係包含將在前述熱電轉換材料的晶片的側面上所形成的焊錫受理層之全部或一部分予以去除的步驟之步驟，較佳為於焊錫受理層之中，同時去除熱電轉換材料的晶片的側面之焊錫受理層的全部及從熱電轉換材料的晶片的側面之壁起的深度方向之一部分的步驟，例如於圖1(b)中，藉由去除在熱電轉換材料的晶片1p的側面2c上所形成的焊錫受理層3，而形成僅在熱電轉換材料的晶片1p之上表面2a及下表面2b具有焊錫受理層3的熱電轉換材料的晶片4p之步驟。 再者，不是僅去除焊錫受理層，而且同時去除從熱電轉換材料的晶片的側面之壁起的深度方向之一部分時，與側面之壁的距離只要能維持熱電轉換材料的晶片之形狀安定性，則沒有特別的限制。藉由成為如此，可容易同樣地形成複數之熱電轉換材料的晶片之形狀。(B) Solder acceptance layer removal step The solder receiving layer removal step is a step including the step of removing all or part of the solder receiving layer formed on the side surface of the aforementioned thermoelectric conversion material wafer, preferably in the solder receiving layer, while removing the thermoelectric conversion material The step of all of the solder receiving layer on the side surface of the wafer and a part of the depth direction from the wall of the side surface of the thermoelectric conversion material, for example, in Figure 1(b), by removing the part of the wafer 1p on the thermoelectric conversion material The solder receiving layer 3 formed on the side surface 2c is a step of forming the thermoelectric conversion material wafer 4p having the solder receiving layer 3 only on the upper surface 2a and the lower surface 2b of the thermoelectric conversion material wafer 1p. Furthermore, when not only removing the solder receiving layer, but also removing part of the depth direction from the side wall of the thermoelectric conversion material wafer, the distance from the side wall can maintain the shape stability of the thermoelectric conversion material wafer at the same time. There are no special restrictions. By doing this, it is possible to easily form a plurality of thermoelectric conversion material wafer shapes in the same manner.

(焊錫受理層去除方法) 作為去除焊錫受理層之方法，雖然依賴於所用的焊錫受理層之材料，但可舉出機械抛光法、化學抛光法、電解抛光法、化學機械抛光(Chemical Mechanical Polishing，CMP抛光)法等之表面抛光方法。 作為機械抛光法，例如可舉出銼刀或砂紙之抛光、安裝有砂紙的帶式砂磨機裝置之抛光、於圓板狀的不織布等之外周面上塗佈抛光劑，邊旋轉邊推壓至焊錫受理層之表面的磨光抛光，或將抛光材(粒子)等混入壓縮機的壓縮空氣等中，噴吹處理的噴砂之抛光、噴射洗滌抛光等。 作為化學抛光法，可舉出藉由使用蝕刻液(過硫酸鹽、過氧化氫-硫酸混合物、無機・有機酸等)等而去除之方法等。 作為電解抛光法，係在鹽酸或硝酸電解液中，藉由交流、高頻交流、三角波交流或直流進行電解之方法。作為電解抛光法所使用之電解液，宜為鹽酸、硝酸、彼等之鹽等的一種或二種以上之混合液。再者，視需要亦可添加硫酸、磷酸、硼酸、銨鹽等。 化學機械抛光法係藉由抛光劑(抛光粒)本身具有的表面化學作用或漿料中所含有的化學成分之作用，使漿料與抛光對象物之相對運動所致的機械抛光(表面去除)效果增大，得到極平滑的抛光面之方法。即，化學(chemical)地溶解抛光表面，使其變質等，幫助抛光粒的機械(mechanical)抛光，相乘地提高抛光速度或品質之方法。 其中，較佳為以機械抛光法、化學抛光法及電解抛光法之表面抛光法的至少一種以上之方法進行。 由於立方體、長方體狀等之單純形狀的面之抛光可效率良好，相較於與其他抛光法，處理中有害氣體的發生亦少，更佳為以機械抛光法進行。於機械抛光法之中，較佳為以銼刀或砂紙等進行抛光之手法、噴砂法，從生產性、去除的確實性之觀點來看，更佳為噴砂法。 去除焊錫受理層之一部分時，在遮掩不去除的部分後，藉由上述的表面抛光方法去除焊錫受理層。(How to remove the solder receiving layer) As a method for removing the solder receiving layer, although it depends on the material of the solder receiving layer used, it can include mechanical polishing, chemical polishing, electrolytic polishing, chemical mechanical polishing (Chemical Mechanical Polishing, CMP polishing) method, etc. Polishing method. As a mechanical polishing method, for example, polishing with a file or sandpaper, polishing with a belt-type sand mill device equipped with sandpaper, coating a polishing agent on the outer peripheral surface of a disc-shaped non-woven cloth, etc., and pressing it while rotating Polishing of the surface of the solder receiving layer, or mixing polishing materials (particles) into the compressed air of the compressor, etc., spraying sandblasting polishing, jet washing polishing, etc. Examples of the chemical polishing method include a method of removing by using an etching solution (persulfate, hydrogen peroxide-sulfuric acid mixture, inorganic/organic acid, etc.). As an electrolytic polishing method, it is a method of electrolysis by alternating current, high frequency alternating current, triangular wave alternating current or direct current in hydrochloric acid or nitric acid electrolyte. The electrolyte used in the electrolytic polishing method is preferably one or a mixture of two or more of hydrochloric acid, nitric acid, and their salts. Furthermore, sulfuric acid, phosphoric acid, boric acid, ammonium salt, etc. may be added as necessary. The chemical mechanical polishing method is mechanical polishing (surface removal) caused by the relative movement of the slurry and the polishing object by the surface chemical effect of the polishing agent (polishing particles) or the effect of the chemical components contained in the slurry. The effect is increased, and a very smooth polished surface is obtained. That is, it is a method to chemically dissolve the polished surface to change its quality, etc., to help the mechanical polishing of the polishing particles, and to synergistically increase the polishing speed or quality. Among them, it is preferably carried out by at least one of the surface polishing methods of the mechanical polishing method, the chemical polishing method, and the electrolytic polishing method. Since the polishing of simple shapes such as cubes and cuboids can be efficient, compared with other polishing methods, there is less harmful gas in the treatment, and it is better to perform mechanical polishing. Among the mechanical polishing methods, a method of polishing with a file, sandpaper, etc., and a sandblasting method are preferable, and from the viewpoint of productivity and the reliability of removal, the sandblasting method is more preferable. When removing a part of the solder receiving layer, the solder receiving layer is removed by the above-mentioned surface polishing method after masking the unremoved part.

於機械抛光法中，使用以銼刀或砂紙等進行抛光之手法時，例如砂紙之號數通常使用100～4000者，可從低號數者起依序抛光。由於使用號數為上述範圍的砂紙，不用說可短時間去除焊錫受理層，也可容易地平坦去除熱電轉換材料的晶片的側面之壁的一部分。In the mechanical polishing method, when using a method of polishing with a file or sandpaper, for example, the number of sandpaper is usually 100 to 4000, and the lower number can be polished in order. Since the sandpaper with the number in the above range is used, it is needless to say that the solder receiving layer can be removed in a short time, and part of the side wall of the wafer of the thermoelectric conversion material can be easily and flatly removed.

作為以銼刀或砂紙等進行抛光之手法，例如可舉出如以下之手法。 以鑷子固定熱電轉換材料的晶片，以經固定於台上的銼刀或砂紙，全部抛光熱電轉換材料的晶片之側面。此時，熱電轉換材料的晶片之側面係以與台呈平行的方式進行抛光。然後，為了能確實地去除，抛光到熱電半導體組成物露出為止。As a method of polishing with a file, sandpaper, etc., the following methods can be mentioned, for example. Fix the wafer of thermoelectric conversion material with tweezers, and polish the sides of the wafer of thermoelectric conversion material with a file or sandpaper fixed on the table. At this time, the side surface of the wafer of thermoelectric conversion material is polished in a manner parallel to the stage. Then, in order to be able to remove it reliably, polishing is performed until the thermoelectric semiconductor composition is exposed.

又，於機械抛光法中，作為噴砂法所用之抛光劑(噴砂材)，使用眾所周知的各種者，例如可舉出玻璃珠、SiC、SiO₂ 、Al₂ O₃ 、ZrO等之粒子。 粒子之平均粒徑通常為1～100μm，較佳為2～80μm，更佳為5～50μm，尤佳為8～40μm。雖然依賴於焊錫受理層及熱電轉換材料的晶片中所用的材料，但從上述來適宜選擇抛光劑，使平均粒徑成為該範圍，不用說可短時間去除焊錫受理層，也可連續地去除熱電轉換材料的晶片的側面之壁面的一部分。 再者，粒子之平均粒徑例如係可藉由庫爾特計數法進行測定。In the mechanical polishing method, various well-known polishing agents (sandblasting materials) used in the sandblasting method are used, and examples include glass beads, SiC, SiO ₂ , Al ₂ O ₃ , ZrO, and other particles. The average particle size of the particles is usually 1-100 μm, preferably 2 to 80 μm, more preferably 5 to 50 μm, and particularly preferably 8 to 40 μm. Although it depends on the material used in the solder receiving layer and the thermoelectric conversion material wafer, the polishing agent is appropriately selected from the above and the average particle size is within this range. Needless to say, the solder receiving layer can be removed in a short time and the thermoelectric can be continuously removed. Part of the wall surface of the side surface of the wafer that converts the material. In addition, the average particle size of the particles can be measured, for example, by the Coulter counting method.

作為以噴砂進行抛光之手法，例如可舉出如以下之手法。 可重疊複數片的熱電轉換材料的晶片，於一側面能露出的模具中，設置熱電轉換材料的晶片。熱電轉換材料的晶片係僅抛光之量從模具突出。對於該突出之熱電轉換材料的晶片，進行噴砂處理，而去除一面的焊錫受理層。同樣地，對於剩餘的其他側面，亦重複噴砂處理，而去除全部的側面之焊錫受理層。As a method of polishing by sandblasting, for example, the following methods can be cited. A plurality of wafers of thermoelectric conversion material can be stacked, and the wafer of thermoelectric conversion material is set in a mold whose one side can be exposed. The wafer of thermoelectric conversion material protrudes from the mold only by the polishing amount. The protruding thermoelectric conversion material wafer is sandblasted to remove the solder receiving layer on one side. Similarly, for the remaining other side surfaces, the sandblasting process is repeated to remove the solder receiving layer on all the side surfaces.

(熱電轉換材料的晶片) 本發明所用之熱電轉換材料的晶片係包含熱電半導體組成物而成。較佳包含由含有熱電半導體材料(以下亦稱為「熱半導體粒子」)、耐熱性樹脂以及離子液體及/或無機離子性化合物的熱電半導體組成物所成之薄膜。(Thermoelectric conversion material wafer) The wafer of the thermoelectric conversion material used in the present invention is composed of a thermoelectric semiconductor composition. Preferably, it includes a thin film made of a thermoelectric semiconductor composition containing a thermoelectric semiconductor material (hereinafter also referred to as "thermal semiconductor particles"), a heat-resistant resin, an ionic liquid and/or an inorganic ionic compound.

(熱電半導體材料) 作為本發明所用的熱電半導體材料，亦即P型熱電轉換材料的晶片、N型熱電轉換材料的晶片中所包含之熱電半導體材料，只要是藉由賦予溫度差而能產生熱電動勢之材料，則沒有特別的限制，例如可使用P型鉍碲化物、N型鉍碲化物等之鉍-碲系熱電半導體材料；GeTe、PbTe等之碲化物系熱電半導體材料；銻-碲系熱電半導體材料；ZnSb、Zn₃ Sb₂ 、Zn₄ Sb₃ 等之鋅-銻系熱電半導體材料；SiGe等之矽-鍺系熱電半導體材料；Bi₂ Se₃ 等之鉍硒化物系熱電半導體材料；β-FeSi₂ 、CrSi₂ 、MnSi_1.73 、Mg₂ Si等之矽化物系熱電半導體材料；氧化物系熱電半導體材料；FeVAl、FeVAlSi、FeVTiAl等之豪斯勒材料、TiS₂ 等之硫化物系熱電半導體材料等。 於此等之中，較佳為鉍-碲系熱電半導體材料、碲化物系熱電半導體材料、銻-碲系熱電半導體材料或鉍硒化物系熱電半導體材料。(Thermoelectric semiconductor material) As the thermoelectric semiconductor material used in the present invention, that is, the thermoelectric semiconductor material contained in the wafer of P-type thermoelectric conversion material and the wafer of N-type thermoelectric conversion material, as long as it can generate heat by imparting a temperature difference There are no special restrictions on the material of the electromotive force. For example, P-type bismuth telluride, N-type bismuth telluride and other bismuth-tellurium thermoelectric semiconductor materials; GeTe, PbTe, etc., telluride-based thermoelectric semiconductor materials; antimony-tellurium Thermoelectric semiconductor materials; _{zinc-antimony thermoelectric semiconductor materials such as ZnSb, Zn 3} Sb ₂ , Zn ₄ Sb ₃ ; silicon-germanium thermoelectric semiconductor materials such as SiGe; Bi ₂ Se ₃ and other bismuth selenide thermoelectric semiconductor materials; β-FeSi ₂ , CrSi ₂ , MnSi _1.73 , Mg ₂ Si and other silicide-based thermoelectric semiconductor materials; oxide-based thermoelectric semiconductor materials; FeVAl, FeVAlSi, FeVTiAl, etc. Hausler materials, TiS ₂ and other sulfide-based thermoelectric materials Semiconductor materials, etc. Among these, bismuth-telluride-based thermoelectric semiconductor materials, telluride-based thermoelectric semiconductor materials, antimony-tellurium-based thermoelectric semiconductor materials, or bismuth selenide-based thermoelectric semiconductor materials are preferred.

再者，從熱電性能之觀點來看，更佳為P型鉍碲化物或N型鉍碲化物等之鉍-碲系熱電半導體材料。 前述P型鉍碲化物係載體為電洞，席貝克係數為正值，例如較宜使用以Bi_X Te₃ Sb_2-X 表示者。此時，X較佳為0＜X≦0.8，更佳為0.4≦X≦0.6。若X大於0且為0.8以下，則席貝克係數與電導率變大，維持作為P型熱電元件的特性而較宜。 又，前述N型鉍碲化物係載體為電子，席貝克係數為負值，例如較宜使用以Bi₂ Te_3-Y Se_Y 表示者。此時，Y較佳為0≦Y≦3(Y=0時：Bi₂ Te₃ )，更佳為0＜Y≦2.7。若Y為0以上3以下，則席貝克係數與電導率變大，維持作為N型熱電元件的特性而較宜。Furthermore, from the standpoint of thermoelectric performance, a bismuth-tellurium-based thermoelectric semiconductor material such as P-type bismuth telluride or N-type bismuth telluride is more preferable. The aforementioned P-type bismuth telluride-based carrier is an electric hole, and the Schiebeck coefficient is a positive value. For example, it is better to use the one represented by Bi _X Te ₃ Sb _2-X . At this time, X is preferably 0<X≦0.8, and more preferably 0.4≦X≦0.6. If X is greater than 0 and 0.8 or less, the Sibeck coefficient and electrical conductivity increase, and it is preferable to maintain the characteristics as a P-type thermoelectric element. In addition, the aforementioned N-type bismuth telluride-based carrier is electrons, and the Schibeck coefficient is a negative value. For example, it is preferable to use the one represented by Bi ₂ Te _3-Y Se _Y. At this time, Y is preferably 0≦Y≦3 (when Y=0: Bi ₂ Te ₃ ), and more preferably 0<Y≦2.7. If Y is 0 or more and 3 or less, the Sibeck coefficient and electrical conductivity increase, and it is preferable to maintain the characteristics as an N-type thermoelectric element.

熱電半導體組成物中使用的熱電半導體粒子，係藉由微粉碎裝置等，將前述的熱電半導體材料粉碎到指定的尺寸為止者。The thermoelectric semiconductor particles used in the thermoelectric semiconductor composition are those obtained by pulverizing the aforementioned thermoelectric semiconductor material to a predetermined size by a fine pulverizing device or the like.

熱電半導體粒子在前述熱電半導體組成物中的摻合量較佳為30～99質量%，更佳為50～96質量%，尤佳為70～95質量%。熱電半導體粒子之摻合量只要為上述範圍內，則席貝克係數(帕耳帖係數之絕對值)大，且抑制電導率之降低，由於僅熱傳導率降低而顯示高的熱電性能，同時得到具有充分皮膜強度、彎曲性之膜而較宜。The blending amount of the thermoelectric semiconductor particles in the aforementioned thermoelectric semiconductor composition is preferably 30 to 99% by mass, more preferably 50 to 96% by mass, and particularly preferably 70 to 95% by mass. As long as the blending amount of thermoelectric semiconductor particles is within the above-mentioned range, the Schibeck coefficient (the absolute value of the Peltier coefficient) is large, and the decrease in electrical conductivity is suppressed. Only the decrease in thermal conductivity results in high thermoelectric performance, and at the same time A film with sufficient film strength and flexibility is preferable.

熱電半導體粒子之平均粒徑較佳為10nm～200 μm，更佳為10nm～30μm，尤佳為50nm～10μm，特佳為1～6μm。若為上述範圍內，則均勻的分散變容易，可提高電導率。 將前述熱電半導體材料粉碎而得到熱電半導體粒子之方法係沒有特別的限定，只要藉由噴射磨機、球磨機、珠磨機、膠體磨機、輥磨機等之眾所周知的微粉碎裝置等，粉碎到指定的尺寸為止即可。 再者，熱電半導體粒子之平均粒徑係藉由雷射繞射式粒度分析裝置(Malvern公司製Mastersizer 3000)測定而得之粒徑分布的中央值。The average particle diameter of the thermoelectric semiconductor particles is preferably 10 nm to 200 μm, more preferably 10 nm to 30 μm, particularly preferably 50 nm to 10 μm, particularly preferably 1 to 6 μm. If it is in the above range, uniform dispersion becomes easier, and conductivity can be improved. The method of pulverizing the aforementioned thermoelectric semiconductor material to obtain thermoelectric semiconductor particles is not particularly limited, as long as it is pulverized to a well-known fine pulverizing device such as a jet mill, a ball mill, a bead mill, a colloid mill, and a roller mill. Only the specified size is required. In addition, the average particle size of the thermoelectric semiconductor particles is the median value of the particle size distribution measured by a laser diffraction particle size analyzer (Mastersizer 3000 manufactured by Malvern).

又，熱電半導體粒子較佳為事先經熱處理者(此處所言的「熱處理」係與本發明中所言之退火處理步驟所進行「退火處理」不同)。藉由進行熱處理，熱電半導體粒子係結晶性升高，再者熱電半導體粒子的表面氧化膜係被去除，因此熱電轉換材料的席貝克係數或帕耳帖係數增大，可更提高熱電性能指數。熱處理係沒有特別的限定，但以在調製熱電半導體組成物之前，不對於熱電半導體粒子造成不良影響之方式，較佳為在氣體流量經控制的氮、氬等之惰性氣體環境下，同樣地在氫等之還原氣體環境下或真空條件下進行，更佳為在惰性氣體及還原氣體的混合氣體環境下進行。具體的溫度條件係依賴於所用的熱電半導體粒子，但通常為粒子的熔點以下之溫度，且較佳為在100～1500℃下進行數分鐘～數十小時。In addition, the thermoelectric semiconductor particles are preferably those that have been heat-treated in advance (the "heat treatment" referred to here is different from the "annealing treatment" performed in the annealing step in the present invention). By performing heat treatment, the crystallinity of the thermoelectric semiconductor particles is increased, and the surface oxide film of the thermoelectric semiconductor particles is removed. Therefore, the Sibeck coefficient or Peltier coefficient of the thermoelectric conversion material is increased, and the thermoelectric performance index can be further improved. The heat treatment system is not particularly limited. However, it is preferable to use an inert gas environment such as nitrogen and argon with a controlled gas flow rate in a manner that does not adversely affect the thermoelectric semiconductor particles before preparing the thermoelectric semiconductor composition. It is carried out under a reducing gas environment such as hydrogen or under a vacuum condition, and more preferably under a mixed gas environment of inert gas and reducing gas. The specific temperature conditions depend on the thermoelectric semiconductor particles used, but are usually a temperature below the melting point of the particles, and preferably at 100 to 1500°C for several minutes to tens of hours.

(耐熱性樹脂) 於本發明所用的熱電半導體組成物中，從將熱電半導體材料在高溫度下進行退火處理之觀點來看，較宜使用耐熱性樹脂。作為熱電半導體材料(熱電半導體粒子)間之黏結劑作用，可提高熱電轉換模組的彎曲性，同時容易藉由塗佈等而形成薄膜。該耐熱性樹脂係沒有特別的限制，但於將包含熱電半導體組成物而成的薄膜，藉由退火處理等而使熱電半導體粒子進行結晶成長時，較佳為不損害作為樹脂的機械強度及熱傳導率等之諸物性而維持的耐熱性樹脂。 從耐熱性更高，且不對於薄膜中的熱電半導體粒子之結晶成長造成不良影響之點來看，前述耐熱性樹脂較佳為聚醯胺樹脂、聚醯胺醯亞胺樹脂、聚醯亞胺樹脂、環氧樹脂，從彎曲性優異之點來看，更佳為聚醯胺樹脂、聚醯胺醯亞胺樹脂、聚醯亞胺樹脂。作為後述之基板，使用聚醯亞胺薄膜時，從與該聚醯亞胺薄膜的密著性等之點來看，作為耐熱性樹脂，更佳為聚醯亞胺樹脂。再者，本發明中所謂的聚醯亞胺樹脂，係將聚醯亞胺及其前驅物總稱。(Heat resistant resin) In the thermoelectric semiconductor composition used in the present invention, a heat-resistant resin is preferably used from the viewpoint of annealing the thermoelectric semiconductor material at a high temperature. As a bonding agent between thermoelectric semiconductor materials (thermoelectric semiconductor particles), it can improve the flexibility of the thermoelectric conversion module, and at the same time, it is easy to form a thin film by coating or the like. The heat-resistant resin system is not particularly limited, but when a thin film containing a thermoelectric semiconductor composition is subjected to annealing treatment or the like to crystallize thermoelectric semiconductor particles, it is preferable not to impair the mechanical strength and thermal conductivity of the resin. It is a heat-resistant resin that maintains various physical properties such as high efficiency. From the viewpoint of higher heat resistance and not adversely affecting the crystal growth of thermoelectric semiconductor particles in the film, the aforementioned heat-resistant resin is preferably polyamide resin, polyimide resin, and polyimide resin. The resin and epoxy resin are more preferably polyamide resin, polyimide resin, and polyimide resin in terms of excellent flexibility. When a polyimide film is used as the substrate described later, from the viewpoint of adhesion to the polyimide film, etc., the heat-resistant resin is more preferably a polyimide resin. Furthermore, the so-called polyimide resin in the present invention is a general term for polyimide and its precursors.

前述耐熱性樹脂係分解溫度較佳為300℃以上。若分解溫度為上述範圍，則如後述，即使將包含熱電半導體組成物而成之薄膜予以退火處理時，也不喪失作為黏結劑的功能，可維持彎曲性。The decomposition temperature of the heat-resistant resin is preferably 300°C or higher. If the decomposition temperature is in the above range, as will be described later, even when a thin film containing the thermoelectric semiconductor composition is annealed, the function as a binder is not lost, and flexibility can be maintained.

又，前述耐熱性樹脂係熱重量測定(TG)的300℃之質量減少率較佳為10%以下，更佳為5%以下，尤佳為1%以下。若質量減少率為上述範圍，則如後述，即使將包含熱電半導體組成物而成之薄膜予以退火處理時，也不喪失作為黏結劑的功能，可維持熱電轉換材料層之彎曲性。In addition, the mass reduction rate at 300°C of the heat-resistant resin-based thermogravimetry (TG) is preferably 10% or less, more preferably 5% or less, and particularly preferably 1% or less. If the mass reduction rate is in the above range, as will be described later, even when the film containing the thermoelectric semiconductor composition is annealed, the function as a binder is not lost, and the flexibility of the thermoelectric conversion material layer can be maintained.

前述耐熱性樹脂在前述熱電半導體組成物中之摻合量為0.1～40質量%，較佳為0.5～20質量%，更佳為1～20質量%，尤佳為2～15質量%。若前述耐熱性樹脂之摻合量為上述範圍內，則具有作為熱電半導體材料的黏結劑之功能，容易形成薄膜，而且得到兼顧高的熱電性能與皮膜強度之膜。The blending amount of the heat-resistant resin in the thermoelectric semiconductor composition is 0.1-40% by mass, preferably 0.5-20% by mass, more preferably 1-20% by mass, and particularly preferably 2-15% by mass. If the blending amount of the heat-resistant resin is within the above range, it has a function as a binder for thermoelectric semiconductor materials, it is easy to form a thin film, and a film with both high thermoelectric performance and film strength can be obtained.

(離子液體) 本發明所用之離子液體係組合陽離子與陰離子而成之熔融鹽，指於-50～400℃之溫度範圍的任一溫度範圍中，可以液體存在之鹽。換言之，離子液體係熔點在-50℃以上且未達400℃之範圍的離子性化合物。離子液體之熔點較佳為-25℃以上200℃以下，更佳為0℃以上150℃以下。離子液體係蒸氣壓極低而為不揮發性，具有優異的熱安定性及電化學安定性，具有黏度低且離子傳導度高等之特徵，因此作為導電輔助劑，可有效果地抑制熱電半導體粒子間的電導率之減低。又，離子液體係顯示以非質子性的離子構造為基礎之高極性，由於與耐熱性樹脂的相溶性優異，可使熱電轉換材料層的晶片之電導率成為均勻。(Ionic liquid) The molten salt formed by combining cations and anions in the ionic liquid system used in the present invention refers to a salt that can exist as a liquid in any temperature range of -50 to 400°C. In other words, the ionic liquid system has an ionic compound whose melting point is above -50°C and does not reach the range of 400°C. The melting point of the ionic liquid is preferably -25°C or higher and 200°C or lower, more preferably 0°C or higher and 150°C or lower. The ionic liquid system has extremely low vapor pressure and is non-volatile, has excellent thermal stability and electrochemical stability, and has the characteristics of low viscosity and high ion conductivity. Therefore, as a conductive auxiliary agent, it can effectively suppress thermoelectric semiconductor particles Decrease the conductivity between the time. In addition, the ionic liquid system exhibits high polarity based on an aprotic ionic structure, and due to its excellent compatibility with the heat-resistant resin, the electrical conductivity of the wafer of the thermoelectric conversion material layer can be made uniform.

離子液體係可使用眾所周知或市售者。例如，可舉出由以下者所構成：吡啶鎓、嘧啶鎓、吡唑鎓、吡唑鎓、哌啶鎓、咪唑鎓等之含氮的環狀陽離子化合物及彼等之衍生物；四烷基銨的胺系陽離子及彼等之衍生物；鏻、三烷基鋶、四烷基鏻等之膦系陽離子及彼等之衍生物；鋰陽離子及其衍生物等之陽離子成分，與Cl^- 、AlCl₄ ^- 、Al₂ Cl₇ ^- 、ClO₄ ^- 等之氯化物離子、Br^- 等之溴化物離子、I^- 等之碘化物離子、BF₄ ^- 、PF₆ ^- 等之氟化物離子、F(HF)_n ^- 等之鹵化物陰離子、NO₃ ^- 、CH₃ COO^- 、CF₃ COO^- 、CH₃ SO₃ ^- 、CF₃ SO₃ ^- 、(FSO₂ )₂ N^- 、(CF₃ SO₂ )₂ N^- 、(CF₃ SO₂ )₃ C^- 、AsF₆ ^- 、SbF₆ ^- 、NbF₆ ^- 、TaF₆ ^- 、F(HF)n^- 、(CN)₂ N^- 、C₄ F₉ SO₃ ^- 、(C₂ F₅ SO₂ )₂ N^- 、C₃ F₇ COO^- 、(CF₃ SO₂ )(CF₃ CO)N^- 等之陰離子成分。As the ionic liquid system, well-known or commercially available ones can be used. For example, the following can be mentioned: pyridinium, pyrimidinium, pyrazolium, pyrazolium, piperidinium, imidazolium and other nitrogen-containing cyclic cationic compounds and their derivatives; tetraalkyl phosphonium, sulfonium trialkyl, tetraalkyl phosphonium cation of the phosphine and whose;; amine derivatives ammonium cations and whose cationic component of a lithium cation and a derivative thereof, and Cl ^{-, _{AlCl 4 -, Al 2 Cl 7}} -, ClO 4 - chloride ions, etc., Br ^-, etc. bromide ion, I ^-, etc. iodide ion, BF ₄ ^-, PF ₆ ^-, etc. fluoride ions, F ( HF) _n ^-, etc. halide _{^{anion, NO 3 -, CH 3 COO}} -, CF 3 COO -, CH 3 SO 3 -, CF 3 SO 3 -, (FSO 2) 2 N -, (CF 3 SO 2) _{^{2 N -, (CF 3 SO}} 2) 3 C -, AsF 6 -, SbF 6 -, NbF 6 -, TaF 6 -, F (HF) n -, (CN) 2 N -, C 4 F 9 SO 3 _{^{-, (C 2 F 5 SO}} 2) 2 N -, C 3 F 7 COO -, (CF 3 SO 2) (CF 3 CO) N - like the anionic component.

於上述離子液體之中，從高溫安定性、熱電半導體粒子及與樹脂的相溶性、抑制熱電半導體粒子間隙的電導率之降低等之觀點來看，離子液體的陽離子成分較佳為包含由吡啶鎓陽離子及其衍生物、咪唑鎓陽離子及其衍生物所選出的至少1種。離子液體的陰離子成分較佳為包含鹵化物陰離子，更佳為包含由Cl^- 、Br^- 及I^- 所選出的至少1種。Among the above-mentioned ionic liquids, from the viewpoints of high temperature stability, thermoelectric semiconductor particles and compatibility with resins, and suppression of the decrease in conductivity of the thermoelectric semiconductor particles, the cation component of the ionic liquid preferably contains pyridinium At least one selected from cation and its derivatives, imidazolium cation and its derivatives. Anionic component of the ionic liquid preferably comprises a halide anion, more preferably comprises a Cl ^-, Br ^- and I ^- the selected at least one kind.

作為陽離子成分為包含吡啶鎓陽離子及其衍生物的離子液體之具體例，可舉出4-甲基-丁基吡啶鎓氯化物、3-甲基-丁基吡啶鎓氯化物、4-甲基-己基吡啶鎓氯化物、3-甲基-己基吡啶鎓氯化物、4-甲基-辛基吡啶鎓氯化物、3-甲基-辛基吡啶鎓氯化物、3,4-二甲基-丁基吡啶鎓氯化物、3,5-二甲基-丁基吡啶鎓氯化物、4-甲基-丁基吡啶鎓四氟硼酸鹽、4-甲基-丁基吡啶鎓六氟磷酸鹽、1-丁基吡啶鎓溴化物、1-丁基-4-甲基吡啶鎓溴化物、1-丁基-4-甲基吡啶鎓六氟磷酸鹽、1-丁基-4-甲基吡啶鎓碘化物等。其中，較佳為1-丁基吡啶鎓溴化物、1-丁基-4-甲基吡啶鎓溴化物、1-丁基-4-甲基吡啶鎓六氟磷酸鹽、1-丁基-4-甲基吡啶鎓碘化物。Specific examples of ionic liquids containing pyridinium cations and derivatives thereof as the cationic component include 4-methyl-butylpyridinium chloride, 3-methyl-butylpyridinium chloride, 4-methyl -Hexylpyridinium chloride, 3-methyl-hexylpyridinium chloride, 4-methyl-octylpyridinium chloride, 3-methyl-octylpyridinium chloride, 3,4-dimethyl- Butylpyridinium chloride, 3,5-dimethyl-butylpyridinium chloride, 4-methyl-butylpyridinium tetrafluoroborate, 4-methyl-butylpyridinium hexafluorophosphate, 1-butylpyridinium bromide, 1-butyl-4-methylpyridinium bromide, 1-butyl-4-methylpyridinium hexafluorophosphate, 1-butyl-4-methylpyridinium Iodide, etc. Among them, 1-butylpyridinium bromide, 1-butyl-4-methylpyridinium bromide, 1-butyl-4-methylpyridinium hexafluorophosphate, 1-butyl-4 -Methylpyridinium iodide.

又，作為陽離子成分為包含咪唑鎓陽離子及其衍生物的離子液體之具體例，可舉出[1-丁基-3-(2-羥基乙基)咪唑鎓溴化物]、[1-丁基-3-(2-羥基乙基)咪唑鎓四氟硼酸鹽]、1-乙基-3-甲基咪唑鎓氯化物、1-乙基-3-甲基咪唑鎓溴化物、1-丁基-3-甲基咪唑鎓氯化物、1-己基-3-甲基咪唑鎓氯化物、1辛基-3-甲基咪唑鎓氯化物、1-癸基-3-甲基咪唑鎓氯化物、1-癸基-3-甲基咪唑鎓溴化物、1-十二基-3-甲基咪唑鎓氯化物、1-十四基-3-甲基咪唑鎓氯化物、1-乙基-3-甲基咪唑鎓四氟硼酸鹽、1-丁基-3-甲基咪唑鎓四氟硼酸鹽、1-己基-3-甲基咪唑鎓四氟硼酸鹽、1-乙基-3-甲基咪唑鎓六氟磷酸鹽、1-丁基-3-甲基咪唑鎓六氟磷酸鹽、1-甲基-3-丁基咪唑鎓甲基硫酸鹽、1,3-二丁基咪唑鎓甲基硫酸鹽等。其中，較佳為[1-丁基-3-(2-羥基乙基)咪唑鎓溴化物]、[1-丁基-3-(2-羥基乙基)咪唑鎓四氟硼酸鹽]。In addition, specific examples of ionic liquids containing imidazolium cations and their derivatives as the cationic component include [1-butyl-3-(2-hydroxyethyl)imidazolium bromide], [1-butyl -3-(2-hydroxyethyl)imidazolium tetrafluoroborate], 1-ethyl-3-methylimidazolium chloride, 1-ethyl-3-methylimidazolium bromide, 1-butyl -3-methylimidazolium chloride, 1-hexyl-3-methylimidazolium chloride, 1-octyl-3-methylimidazolium chloride, 1-decyl-3-methylimidazolium chloride, 1-decyl-3-methylimidazolium bromide, 1-dodecyl-3-methylimidazolium chloride, 1-tetradecyl-3-methylimidazolium chloride, 1-ethyl-3 -Methylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium tetrafluoroborate, 1-hexyl-3-methylimidazolium tetrafluoroborate, 1-ethyl-3-methyl Imidazolium hexafluorophosphate, 1-butyl-3-methylimidazolium hexafluorophosphate, 1-methyl-3-butylimidazolium methyl sulfate, 1,3-dibutylimidazolium methyl Sulfate etc. Among them, [1-butyl-3-(2-hydroxyethyl)imidazolium bromide] and [1-butyl-3-(2-hydroxyethyl)imidazolium tetrafluoroborate] are preferred.

上述離子液體係電導率較佳為10^-7 S/cm以上，更佳為10^-6 S/cm以上。若電導率為上述範圍，則作為導電輔助劑，可有效果地抑制熱電半導體粒子間的電導率之減低。The conductivity of the ionic liquid system is preferably 10 ^-7 S/cm or more, more preferably 10 ^-6 S/cm or more. If the electrical conductivity is in the above range, as a conductive auxiliary agent, the decrease in electrical conductivity between the thermoelectric semiconductor particles can be effectively suppressed.

又，上述離子液體係分解溫度較佳為300℃以上。若分解溫度為上述範圍，則如後述，即使將包含熱電半導體組成物而成之薄膜予以退火處理時，也可維持作為導電輔助劑之效果。In addition, the decomposition temperature of the ionic liquid system is preferably 300°C or higher. If the decomposition temperature is in the above range, as described later, even when a thin film including a thermoelectric semiconductor composition is annealed, the effect as a conductive auxiliary agent can be maintained.

另外，上述離子液體係熱重量測定(TG)的300℃之質量減少率較佳為10%以下，更佳為5%以下，尤佳為1%以下。若質量減少率為上述範圍，則如後述，即使將包含熱電半導體組成物而成之薄膜予以退火處理時，也可維持作為導電輔助劑之效果。In addition, the mass reduction rate at 300° C. of the above-mentioned ionic liquid system by thermogravimetry (TG) is preferably 10% or less, more preferably 5% or less, and particularly preferably 1% or less. If the mass reduction rate is in the above range, as will be described later, even when a thin film including a thermoelectric semiconductor composition is annealed, the effect as a conductive auxiliary agent can be maintained.

前述離子液體在前述熱電半導體組成物中之摻合量較佳為0.01～50質量%，更佳為0.5～30質量%，尤佳為1.0～20質量%。若前述離子液體之摻合量為上述之範圍內，則有效果地抑制電導率之降低，得到具有高的熱電性能之膜。The blending amount of the ionic liquid in the thermoelectric semiconductor composition is preferably 0.01-50% by mass, more preferably 0.5-30% by mass, and particularly preferably 1.0-20% by mass. If the blending amount of the aforementioned ionic liquid is within the above-mentioned range, the decrease in electrical conductivity can be effectively suppressed, and a film with high thermoelectric performance can be obtained.

(無機離子性化合物) 本發明所用之無機離子性化合物係至少由陽離子與陰離子所構成之化合物。無機離子性化合物係在室溫下為固體，在400～900℃之溫度範圍的任一溫度中具有熔點，具有離子傳導度高等之特徵，因此作為導電輔助劑，可抑制熱電半導體粒子間的電導率之減低。(Inorganic ionic compound) The inorganic ionic compound used in the present invention is a compound composed of at least cations and anions. Inorganic ionic compounds are solid at room temperature, have a melting point at any temperature in the temperature range of 400 to 900 ℃, and have the characteristics of high ion conductivity. Therefore, as a conductive auxiliary agent, it can inhibit the conduction between thermoelectric semiconductor particles. The rate of reduction.

作為陽離子，使用金屬陽離子。 作為金屬陽離子，例如可舉出鹼金屬陽離子、鹼土類金屬陽離子、典型金屬陽離子及過渡金屬陽離子，更佳為鹼金屬陽離子或鹼土類金屬陽離子。 作為鹼金屬陽離子，例如可舉出Li⁺ 、Na⁺ 、K⁺ 、Rb⁺ 、Cs⁺ 及Fr⁺ 等。 作為鹼土類金屬陽離子，例如可舉Mg²⁺ 、Ca²⁺ 、Sr²⁺ 及Ba²⁺ 等。As the cation, a metal cation is used. Examples of the metal cation include alkali metal cations, alkaline earth metal cations, typical metal cations, and transition metal cations, and alkali metal cations or alkaline earth metal cations are more preferred. Examples of alkali metal cations include Li ⁺ , Na ⁺ , K ⁺ , Rb ⁺ , Cs ^+, and Fr ⁺ . Examples of alkaline earth metal cations include Mg ²⁺ , Ca ²⁺ , Sr ²⁺ and Ba ²⁺ .

作為陰離子，例如可舉出F^- 、Cl^- 、Br^- 、I^- 、OH^- 、CN^- 、NO₃ ^- 、NO₂ ^- 、ClO^- 、ClO₂ ^- 、ClO₃ ^- 、ClO₄ ^- 、CrO₄ ^2- 、HSO₄ ^- 、SCN^- 、BF₄ ^- 、PF₆ ^- 等。Examples of the anion, and examples thereof include ^{F -, Cl -, Br -} , I -, OH -, CN -, NO 3 -, NO 2 -, ClO -, ClO 2 -, ClO 3 -, ClO 4 -, CrO 4 _{^{2-, HSO 4 -, SCN -}} , BF 4 -, PF 6 - and the like.

無機離子性化合物係可使用眾所周知或市售者。例如，可舉出由以下者所構成：鉀陽離子、鈉陽離子或鋰陽離子等之陽離子成分，與Cl^- 、AlCl₄ ^- 、Al₂ Cl₇ ^- 、ClO₄ ^- 等之氯化物離子、Br^- 等之溴化物離子、I^- 等之碘化物離子、BF₄ ^- 、PF₆ ^- 等之氟化物離子、F(HF)_n ^- 等之鹵化物陰離子、NO₃ ^- 、OH^- 、CN^- 等之陰離子成分。As the inorganic ionic compound, a well-known or commercially available one can be used. For example, the following may be mentioned is constituted by: potassium cation, a lithium cation, sodium cation or the cationic components and the like, and _{^{Cl -, AlCl 4 -, Al}} 2 Cl 7 -, ClO 4 - , etc. chloride ion, Br ^-, etc. the bromide ion, I ^-, etc. iodide ion, BF ₄ ^-, PF ₆ ^-, etc. fluoride ions, F (HF) _n ^-, etc. halide _{^{anion, NO 3 -, OH -,}} CN - anion, etc. ingredient.

於上述無機離子性化合物之中，從高溫安定性、熱電半導體粒子及與樹脂的相溶性、抑制熱電半導體粒子間隙的電導率之降低等之觀點來看，無機離子性化合物的陽離子成分較佳為包含由鉀、鈉及鋰所選出的至少1種。又，無機離子性化合物的陰離子成分較佳為包含鹵化物陰離子，更佳為包含由Cl^- 、Br^- 及I^- 所選出的至少1種。Among the above-mentioned inorganic ionic compounds, the cationic component of the inorganic ionic compound is preferably from the viewpoints of high temperature stability, thermoelectric semiconductor particles and compatibility with resins, and suppression of the decrease in the conductivity of the thermoelectric semiconductor particles. Contains at least one selected from potassium, sodium, and lithium. Further, the inorganic anion component of the ionic compound is preferably a halide anion comprises, more preferably comprises a Cl ^-, Br ^- and I ^- the selected at least one kind.

作為陽離子成分為包含鉀陽離子的無機離子性化合物之具體例，可舉出KBr、KI、KCl、KF、KOH、K₂ CO₃ 等。其中，較佳為KBr、KI。 作為陽離子成分為包含鈉陽離子的無機離子性化合物之具體例，可舉出NaBr、NaI、NaOH、NaF、Na₂ CO₃ 等。其中，較佳為NaBr、NaI。 作為陽離子成分為包含鋰陽離子的無機離子性化合物之具體例，可舉出LiF、LiOH、LiNO₃ 等。其中，較佳LiF、LiOH。Specific examples of the cationic component being an inorganic ionic compound containing potassium cations include KBr, KI, KCl, KF, KOH, K ₂ CO ₃ and the like. Among them, KBr and KI are preferred. Specific examples of the cationic component being an inorganic ionic compound containing sodium cations include NaBr, NaI, NaOH, NaF, Na ₂ CO ₃ and the like. Among them, NaBr and NaI are preferred. Specific examples of the cationic component being an inorganic ionic compound containing lithium cations include LiF, LiOH, LiNO ₃ and the like. Among them, LiF and LiOH are preferred.

上述無機離子性化合物係電導率較佳為10^-7 S/cm以上，更佳為10^-6 S/cm以上。若電導率為上述範圍，則作為導電輔助劑，可有效果地抑制熱電半導體粒子間的電導率之減低。The conductivity of the inorganic ionic compound system is preferably 10 ^-7 S/cm or more, more preferably 10 ^-6 S/cm or more. If the electrical conductivity is in the above range, as a conductive auxiliary agent, the decrease in electrical conductivity between the thermoelectric semiconductor particles can be effectively suppressed.

又，上述無機離子性化合物係分解溫度較佳為400℃以上。若分解溫度為上述範圍，則如後述，即使將包含熱電半導體組成物而成之薄膜予以退火處理時，也可維持作為導電輔助劑之效果。In addition, the decomposition temperature of the inorganic ionic compound system is preferably 400°C or higher. If the decomposition temperature is in the above range, as will be described later, even when a thin film including a thermoelectric semiconductor composition is annealed, the effect as a conductive auxiliary agent can be maintained.

另外，上述無機離子性化合物係熱重量測定(TG)的400℃之質量減少率較佳為10%以下，更佳為5%以下，尤佳為1%以下。若質量減少率為上述範圍，則如後述，即使將包含熱電半導體組成物而成之薄膜予以退火處理時，也可維持作為導電輔助劑之效果。In addition, the mass reduction rate at 400° C. of the inorganic ionic compound based on thermogravimetry (TG) is preferably 10% or less, more preferably 5% or less, and particularly preferably 1% or less. If the mass reduction rate is in the above range, as will be described later, even when a thin film including a thermoelectric semiconductor composition is annealed, the effect as a conductive auxiliary agent can be maintained.

前述無機離子性化合物在前述熱電半導體組成物中之摻合量較佳0.01～50質量%，更佳為0.5～30質量%，尤佳為1.0～10質量%。若前述無機離子性化合物之摻合量為上述範圍內，則有效果地抑制電導率之降低，結果得到熱電性能升高之膜。 再者，併用無機離子性化合物與離子液體時，於前述熱電半導體組成物中，無機離子性化合物及離子液體之含量的總量較佳為0.01～50質量%，更佳為0.5～30質量%，尤佳為1.0～10質量%。The blending amount of the inorganic ionic compound in the thermoelectric semiconductor composition is preferably 0.01-50% by mass, more preferably 0.5-30% by mass, and particularly preferably 1.0-10% by mass. If the blending amount of the aforementioned inorganic ionic compound is within the above-mentioned range, the decrease in electrical conductivity is effectively suppressed, and as a result, a film with improved thermoelectric performance is obtained. Furthermore, when an inorganic ionic compound and an ionic liquid are used in combination, the total content of the inorganic ionic compound and the ionic liquid in the thermoelectric semiconductor composition is preferably 0.01-50% by mass, more preferably 0.5-30% by mass , Particularly preferably 1.0-10% by mass.

(其他添加劑) 於本發明所用之熱電半導體組成物中，在上述以外之成分以外，視需要亦可更包含分散劑、造膜助劑、光安定劑、抗氧化劑、增黏劑、可塑劑、著色劑、樹脂安定劑、填充劑、顏料、導電性填料、導電性高分子、硬化劑等之其他添加劑。此等之添加劑係可單獨1種或組合2種以上使用。(Other additives) In the thermoelectric semiconductor composition used in the present invention, in addition to the above-mentioned components, if necessary, it may further contain a dispersant, a film forming aid, a light stabilizer, an antioxidant, a tackifier, a plasticizer, a colorant, and a resin. Stabilizers, fillers, pigments, conductive fillers, conductive polymers, hardeners and other additives. These additives can be used alone or in combination of two or more.

(熱電半導體組成物之調製方法) 本發明所用的熱電半導體組成物之調製方法係沒有特別的限制，只要藉由超音波均質機、螺旋混合機、行星式混合機、分散器、複合混合機等眾所周知之方法，添加前述熱電半導體粒子、前述耐熱性樹脂、前述離子液體及無機離子性化合物之一者或兩者，視需要的前述其他添加劑，更且溶劑，使其混合分散，調製該熱電半導體組成物即可。 作為前述溶劑，例如可舉出甲苯、醋酸乙酯、甲基乙基酮、醇、四氫呋喃、甲基吡咯啶酮、乙基賽珞蘇等之溶劑等。此等之溶劑係可單獨使用1種，也可混合2種以上使用。作為熱電半導體組成物之固體成分濃度，只要該組成物適合塗佈的黏度即可，並沒有特別的限制。(Preparation method of thermoelectric semiconductor composition) The preparation method of the thermoelectric semiconductor composition used in the present invention is not particularly limited, as long as the aforementioned thermoelectric semiconductor particles are added by well-known methods such as ultrasonic homogenizers, spiral mixers, planetary mixers, dispersers, compound mixers, etc. , One or both of the heat-resistant resin, the ionic liquid, and the inorganic ionic compound, as needed, the other additives, and a solvent, can be mixed and dispersed to prepare the thermoelectric semiconductor composition. Examples of the aforementioned solvent include solvents such as toluene, ethyl acetate, methyl ethyl ketone, alcohol, tetrahydrofuran, methyl pyrrolidone, and ethyl serosol. These solvents can be used alone or in combination of two or more. The solid content concentration of the thermoelectric semiconductor composition is not particularly limited as long as the composition is suitable for coating viscosity.

(熱電轉換材料的晶片之製造方法) 前述包含熱電半導體組成物而成之薄膜，係在一態樣中，可藉由在犧牲層上塗佈前述熱電半導體組成物，進行乾燥而形成。(Method of manufacturing thermoelectric conversion material wafer) The aforementioned thin film containing the thermoelectric semiconductor composition is, in one aspect, formed by coating the aforementioned thermoelectric semiconductor composition on the sacrificial layer and drying it.

(犧牲層) 於本發明所用的熱電轉換材料的晶片之製造方法中，較佳為使用犧牲層。 犧牲層係用於作為將熱電轉換材料的晶片形成自立膜者，設於基板與熱電轉換材料的晶片之間，於退火處理後，具有剝離熱電轉換材料的晶片之功能。 作為構成犧牲層之材料，可在退火處理後消失，也可殘留，只要結果不對於熱電轉換材料的晶片之特性造成任何影響，具有能剝離熱電轉換材料的晶片之功能即可，較佳為兼備任一功能之樹脂、脫模劑。(Sacrificial layer) In the manufacturing method of the thermoelectric conversion material wafer used in the present invention, it is preferable to use a sacrificial layer. The sacrificial layer is used to form a self-supporting film from a wafer of thermoelectric conversion material. It is provided between the substrate and the wafer of thermoelectric conversion material. After annealing, it has the function of peeling off the wafer of thermoelectric conversion material. As the material constituting the sacrificial layer, it may disappear after annealing treatment or may remain, as long as the result does not have any influence on the characteristics of the thermoelectric conversion material wafer, and it has the function of peeling off the thermoelectric conversion material wafer, preferably both Any functional resin, release agent.

(樹脂) 作為構成本發明所用之犧牲層的樹脂，並沒有特別的限制，可使用熱塑性樹脂或硬化性樹脂。 其中，從可在犧牲層上形成熱電轉換材料的晶片，即使於高溫度下之退火處理後，也可使熱電轉換材料的晶片成為自立膜而容易地剝離之觀點來看，較佳為熱塑性樹脂，較佳為聚甲基丙烯酸甲酯、聚苯乙烯、聚乙烯醇、聚乙烯吡咯啶酮、乙基纖維素，從材料成本、剝離性、熱電轉換材料之特性維持之觀點來看，更佳為聚甲基丙烯酸甲酯、聚苯乙烯。(Resin) The resin constituting the sacrificial layer used in the present invention is not particularly limited, and a thermoplastic resin or a curable resin can be used. Among them, from the viewpoint that the wafer of thermoelectric conversion material can be formed on the sacrificial layer, even after annealing at a high temperature, the wafer of thermoelectric conversion material can become a self-supporting film and can be easily peeled off. Thermoplastic resin is preferred , Preferably polymethyl methacrylate, polystyrene, polyvinyl alcohol, polyvinylpyrrolidone, ethyl cellulose, and more preferably from the viewpoint of material cost, releasability, and property maintenance of thermoelectric conversion materials It is polymethyl methacrylate and polystyrene.

又，前述樹脂係熱重量測定(TG)的後述退火處理溫度下之質量減少率較佳為90%以上，更佳為95%以上，尤佳為99%以上。若質量減少率為上述範圍，則如後述，即使將熱電轉換材料的晶片予以退火處理時，也不喪失能剝離熱電轉換材料的晶片之功能。In addition, the mass reduction rate of the resin-based thermogravimetry (TG) at the annealing temperature described later is preferably 90% or more, more preferably 95% or more, and particularly preferably 99% or more. If the mass reduction rate is in the above range, as will be described later, even when the wafer of thermoelectric conversion material is annealed, the function of peeling the wafer of thermoelectric conversion material will not be lost.

(脫模劑) 作為構成本發明所用之犧牲層的脫模劑，並沒有特別的限制，可舉出氟系脫模劑(含氟原子的化合物；例如，聚四氟乙烯等)、聚矽氧系脫模劑(聚矽氧化合物；例如，聚矽氧樹脂、具有聚氧化烯單元的聚有機矽氧烷等)、高級脂肪酸或其鹽(例如，金屬鹽等)、高級脂肪酸酯、高級脂肪酸醯胺等。 其中，從在犧牲層上可形成熱電轉換材料的晶片，即使在高溫度下之退火處理後，也可使熱電轉換材料的晶片作為自立膜而容易地剝離(脫模)之觀點來看，較佳為氟系脫模劑、聚矽氧系脫模劑，從材料成本、剝離性、熱電轉換材料之特性的維持之觀點來看，更佳為氟系脫模劑。(Release agent) The release agent constituting the sacrificial layer used in the present invention is not particularly limited. Examples include fluorine-based release agents (compounds containing fluorine atoms; for example, polytetrafluoroethylene, etc.), and silicone-based release agents. (Polysiloxane compounds; for example, polysiloxane resins, polyorganosiloxanes having polyoxyalkylene units, etc.), higher fatty acids or their salts (for example, metal salts, etc.), higher fatty acid esters, higher fatty acid amides, etc. . Among them, from the viewpoint that the wafer of thermoelectric conversion material can be formed on the sacrificial layer, even after annealing at high temperature, the wafer of thermoelectric conversion material can be easily peeled off (released) as a self-supporting film. A fluorine-based mold release agent and a silicone-based mold release agent are preferred, and a fluorine-based mold release agent is more preferred from the viewpoint of material cost, releasability, and maintenance of the characteristics of the thermoelectric conversion material.

犧牲層的厚度較佳為10nm～15μm，更佳為50nm～10μm，尤佳為200nm～8μm。若犧牲層的厚度在該範圍，則退火處理後之剝離變容易，且容易維持剝離後之熱電轉換材料的晶片之熱電性能。 特別地，使用樹脂時之犧牲層的厚度較佳為50nm～15μm，更佳為100nm～10μm，尤佳為500nm～8μm。若使用樹脂時之犧牲層的厚度在該範圍，則退火處理後之剝離變容易，且容易維持剝離後之熱電轉換材料的晶片之熱電性能。再者，即使於犧牲層上更層合有其他層時，也容易維持自立膜。 同樣地，使用脫模劑時之犧牲層的厚度較佳為10nm～5μm，更佳為50nm～1μm，尤佳為100nm～0.5μm，特佳為200nm～0.1μm。若使用脫模劑時之犧牲層的厚度在該範圍，則退火處理後之剝離變容易，且容易維持剝離後之熱電轉換材料的晶片之熱電性能。The thickness of the sacrificial layer is preferably 10 nm to 15 μm, more preferably 50 nm to 10 μm, and particularly preferably 200 nm to 8 μm. If the thickness of the sacrificial layer is in this range, peeling after annealing treatment becomes easy, and it is easy to maintain the thermoelectric performance of the wafer of the thermoelectric conversion material after peeling. In particular, the thickness of the sacrificial layer when resin is used is preferably 50 nm to 15 μm, more preferably 100 nm to 10 μm, and particularly preferably 500 nm to 8 μm. If the thickness of the sacrificial layer when using resin is in this range, peeling after annealing treatment becomes easier, and it is easy to maintain the thermoelectric performance of the wafer of the thermoelectric conversion material after peeling. Furthermore, even when another layer is further laminated on the sacrificial layer, the self-supporting film is easily maintained. Similarly, the thickness of the sacrificial layer when the release agent is used is preferably 10 nm to 5 μm, more preferably 50 nm to 1 μm, particularly preferably 100 nm to 0.5 μm, particularly preferably 200 nm to 0.1 μm. If the thickness of the sacrificial layer when using the release agent is in this range, peeling after annealing treatment becomes easier, and it is easy to maintain the thermoelectric performance of the wafer of the thermoelectric conversion material after peeling.

犧牲層之形成係使用前述樹脂或脫模劑進行。 作為形成犧牲層之方法，可舉出在基板上以浸塗法、旋塗法、噴塗法、凹版塗佈法、模塗法、刮刀法等之各種塗佈法。按照所用的樹脂、脫模劑之物性等而適宜選擇。The formation of the sacrificial layer is performed using the aforementioned resin or release agent. As a method of forming the sacrificial layer, various coating methods such as dip coating, spin coating, spray coating, gravure coating, die coating, and doctor blade method on the substrate can be cited. It is appropriately selected according to the physical properties of the resin and release agent used.

(基板) 作為基板，可舉出玻璃、矽、陶瓷、金屬或塑膠等。從在高溫度下進行退火處理之觀點來看，較佳為玻璃、矽、陶瓷、金屬，從與犧牲層的密著性、材料成本、熱處理後的尺寸安定性之觀點來看，更佳為使用玻璃、矽、陶瓷。 從製程及尺寸安定性之觀點來看，前述基板的厚度較佳為100～1200μm，更佳為200～800μm，尤佳為400～700 μm。(Substrate) As the substrate, glass, silicon, ceramic, metal, plastic, etc. can be cited. From the viewpoint of annealing treatment at high temperature, glass, silicon, ceramics, and metal are preferred. From the viewpoint of adhesion to the sacrificial layer, material cost, and dimensional stability after heat treatment, it is more preferred. Use glass, silicon, ceramics. From the viewpoint of process and dimensional stability, the thickness of the aforementioned substrate is preferably 100-1200 μm, more preferably 200-800 μm, and particularly preferably 400-700 μm.

作為將熱電半導體組成物塗佈於基板上之方法，可舉出網版印刷法、柔版印刷法、凹版印刷法、旋塗法、浸塗法、模塗法、噴塗法、棒塗法、刮刀法等眾所周知之方法，並沒有特別的限制。將塗膜形成圖型狀時，使用具有所欲圖型的網版，較佳為使用能簡便地形成圖型之網版印刷、模板印刷、狹縫模具塗佈等。 接著，藉由乾燥所得之塗膜，而形成薄膜，但作為乾燥方法，可採用熱風乾燥法、熱輥乾燥法、紅外線照射法等習知的乾燥方法。加熱溫度通常為80～150℃，加熱時間雖然隨著加熱方法而不同，但通常為數秒～數十分鐘。 又，於熱電半導體組成物之調製中使用溶劑時，加熱溫度只要是所使用的溶劑能乾燥之溫度範圍，則沒有特別的限制。As a method of coating the thermoelectric semiconductor composition on the substrate, there can be mentioned screen printing method, flexographic printing method, gravure printing method, spin coating method, dip coating method, die coating method, spraying method, bar coating method, There are no special restrictions on well-known methods such as the spatula method. When the coating film is formed into a pattern, a screen plate having a desired pattern is used, and it is preferable to use screen printing, stencil printing, slit die coating, etc., which can easily form a pattern. Next, the obtained coating film is dried to form a thin film. However, as the drying method, a conventional drying method such as a hot air drying method, a hot roll drying method, and an infrared irradiation method can be used. The heating temperature is usually 80 to 150°C, and the heating time varies depending on the heating method, but it is usually several seconds to several tens of minutes. In addition, when a solvent is used in the preparation of the thermoelectric semiconductor composition, the heating temperature is not particularly limited as long as the solvent can be dried.

前述包含熱電半導體組成物而成之薄膜的厚度係沒有特別的限制，但從熱電性能與皮膜強度之點來看，較佳為100nm～1000μm，更佳為300nm～600μm，尤佳為5～400μm。The thickness of the aforementioned thin film comprising the thermoelectric semiconductor composition is not particularly limited, but from the viewpoint of thermoelectric performance and film strength, it is preferably 100 nm to 1000 μm, more preferably 300 nm to 600 μm, and particularly preferably 5 to 400 μm .

熱電轉換材料的晶片係在作為薄膜形成後，進行退火處理。藉由進行退火處理，使熱電性能安定化，同時可使薄膜中的熱電半導體粒子進行結晶成長，可更提高熱電性能。The thermoelectric conversion material wafer is formed as a thin film and then annealed. The annealing treatment stabilizes the thermoelectric performance, and at the same time allows the thermoelectric semiconductor particles in the film to crystallize, which can further improve the thermoelectric performance.

退火處理係沒有特別的限定，但通常在氣體流量經控制之氮、氬等惰性氣體環境下、還原氣體環境下或真空條件下進行，雖然依賴於熱電半導體組成物中使用的耐熱性樹脂、離子液體、無機離子性化合物、作為犧牲層使用的樹脂、脫模劑之耐熱溫度等，但退火處理之溫度通常為100～600℃，進行數分鐘～數十小時，較佳在250～450℃，進行數分鐘～數十小時。The annealing treatment system is not particularly limited, but it is usually carried out under an inert gas atmosphere such as nitrogen and argon with controlled gas flow, a reducing gas atmosphere, or a vacuum condition, although it depends on the heat-resistant resin and ion used in the thermoelectric semiconductor composition. Liquid, inorganic ionic compound, resin used as sacrificial layer, heat resistance temperature of release agent, etc., but the temperature of annealing treatment is usually 100-600°C, for several minutes to tens of hours, preferably 250-450°C, It takes several minutes to tens of hours.

作為所得之熱電轉換材料的晶片之剝離方法，只要是在將熱電轉換材料的晶片予以退火處理後，從犧牲層可剝離熱電轉換材料的晶片之方法，則沒有特別的限制，可從犧牲層將熱電轉換材料的複數之晶片，以1片1片的單片之形態來剝離，也可以複數的晶片之形態成批地剝離。As a method of peeling the obtained thermoelectric conversion material wafer, as long as it is a method of peeling the thermoelectric conversion material wafer from the sacrificial layer after annealing the thermoelectric conversion material wafer, there is no particular limitation. The plural wafers of the thermoelectric conversion material are peeled in the form of a single sheet, or the plural wafers may be peeled in batch.

於本發明中，作為其他態樣，可藉由圖型框配置/剝離法，使用前述熱電半導體組成物，製造熱電轉換材料的晶片。In the present invention, as another aspect, the thermoelectric semiconductor composition can be used to manufacture a thermoelectric conversion material wafer by a pattern frame placement/peeling method.

(圖型框配置/剝離法) 所謂圖型框配置/剝離法，就是在基板上設置具有分開的開口部之圖型框，於前述開口部中填充熱電半導體組成物，進行乾燥，將前述圖型框從基板上剝離，而形成已反映圖型框的開口部形狀之形狀控制性優異的熱電轉換材料層之方法，藉此，得到形狀控制性優異之熱電轉換材料的晶片。 作為製造步驟，包含：在基板上設置具有開口部的圖型框之步驟，於前述開口部中填充前述熱電半導體組成物之步驟，乾燥前述開口部中所填充的前述熱電半導體組成物，形成熱電轉換材料層之步驟，及將前述圖型框從基板上剝離之步驟。 使用圖式，具體地說明使用圖型框配置/剝離法之熱電轉換材料層之製造方法的一例。 圖2係依步驟順序顯示圖型框配置/剝離法之熱電轉換材料的晶片之製造方法的一例之說明圖， (a)係顯示於基板上使圖型框呈對向的態樣之剖面圖，準備由不鏽鋼12’所成之具有開口13s、開口部13、開口部深度(圖型框厚)13d的圖型框12，使與基板11呈對向； (b)係將圖型框設於基板上後之剖面圖，將圖型框12設於基板11上； (c)係在圖型框的開口部中填充熱電轉換材料層後之剖面圖，於在(b)所準備之由不鏽鋼12’所成的圖型框12之具有開口13s的開口部13中，將包含P型熱電半導體材料的熱電半導體組成物及包含N型熱電半導體材料的熱電半導體組成物分別填充至指定的開口部13內，乾燥在開口部13中所填充之包含P型熱電半導體材料的熱電半導體組成物及包含N型熱電半導體材料的熱電半導體組成物，形成P型熱電轉換材料層14b、N型熱電轉換材料層14a； (d)係顯示將圖型框從經填充的熱電轉換材料層來剝離，僅得到熱電轉換材料層之態樣的剖面圖，將圖型框12從所形成的P型熱電轉換材料層14b、N型熱電轉換材料層14a來剝離，得到作為自立層的P型熱電轉換材料的晶片14p、N型熱電轉換材料的晶片14n。 作為乾燥方法，可採用熱風乾燥法、熱輥乾燥法、紅外線照射法等習知的乾燥方法。加熱溫度通常為80～150℃，加熱時間係隨著加熱方法而不同，但通常為數秒～數十分鐘。 又，於熱電半導體組成物之調製中使用溶劑時，加熱溫度只要是所使用的溶劑能乾燥之溫度範圍，則沒有特別的限制。 藉由上述，可得到用於熱電轉換模組的本發明之熱電轉換材料的晶片。 再者，關於包含P型熱電半導體材料的熱電半導體組成物及包含N型熱電半導體材料的熱電半導體組成物對於開口部之填充，並沒有特別的限制，可僅填充包含P型熱電半導體材料的熱電半導體組成物，或也可僅填充包含N型熱電半導體材料的熱電半導體組成物。 如此地，藉由圖型框配置/剝離法，可容易得到形狀控制性優異之熱電轉換材料的晶片。(Plot frame placement/stripping method) The so-called pattern frame placement/peeling method is to provide a pattern frame with separate openings on a substrate, fill the opening with a thermoelectric semiconductor composition, dry, and peel the pattern frame from the substrate to form The method of the thermoelectric conversion material layer having excellent shape controllability of the shape of the opening of the pattern frame has been reflected, thereby obtaining a thermoelectric conversion material wafer having excellent shape controllability. The manufacturing steps include: a step of providing a pattern frame with an opening on a substrate, a step of filling the opening with the thermoelectric semiconductor composition, and drying the thermoelectric semiconductor composition filled in the opening to form a thermoelectric The step of converting the material layer, and the step of peeling the aforementioned pattern frame from the substrate. Using drawings, an example of a method of manufacturing a thermoelectric conversion material layer using the pattern frame placement/peeling method will be specifically explained. Fig. 2 is an explanatory diagram showing an example of a manufacturing method of a thermoelectric conversion material wafer by the pattern frame placement/stripping method in the order of steps, (a) A cross-sectional view showing the pattern frame facing each other on the substrate. Prepare a drawing made of stainless steel 12' with openings 13s, openings 13, and opening depth (pattern frame thickness) 13d The frame 12 is opposite to the base plate 11; (b) is a cross-sectional view after the pattern frame is set on the substrate, and the pattern frame 12 is set on the substrate 11; (c) is a cross-sectional view after filling the thermoelectric conversion material layer in the opening of the pattern frame, in the opening 13 with the opening 13s of the pattern frame 12 made of stainless steel 12' prepared in (b) , The thermoelectric semiconductor composition containing the P-type thermoelectric semiconductor material and the thermoelectric semiconductor composition containing the N-type thermoelectric semiconductor material are respectively filled into the designated opening 13, and the P-type thermoelectric semiconductor material filled in the opening 13 is dried The thermoelectric semiconductor composition and the thermoelectric semiconductor composition containing the N-type thermoelectric semiconductor material form a P-type thermoelectric conversion material layer 14b and an N-type thermoelectric conversion material layer 14a; (d) is a cross-sectional view showing that the pattern frame is peeled from the filled thermoelectric conversion material layer, and only the thermoelectric conversion material layer is obtained. The pattern frame 12 is removed from the formed P-type thermoelectric conversion material layer 14b, The N-type thermoelectric conversion material layer 14a is peeled off to obtain a P-type thermoelectric conversion material wafer 14p and an N-type thermoelectric conversion material wafer 14n as a self-supporting layer. As the drying method, a conventional drying method such as a hot air drying method, a hot roll drying method, and an infrared irradiation method can be used. The heating temperature is usually 80 to 150°C, and the heating time varies depending on the heating method, but it is usually several seconds to several tens of minutes. In addition, when a solvent is used in the preparation of the thermoelectric semiconductor composition, the heating temperature is not particularly limited as long as the solvent can be dried. Through the above, a chip of the thermoelectric conversion material of the present invention used in a thermoelectric conversion module can be obtained. Furthermore, there are no particular restrictions on the filling of openings with regard to the thermoelectric semiconductor composition containing P-type thermoelectric semiconductor material and the thermoelectric semiconductor composition containing N-type thermoelectric semiconductor material, and only the thermoelectric semiconductor composition containing P-type thermoelectric semiconductor material can be filled. The semiconductor composition, or only a thermoelectric semiconductor composition containing an N-type thermoelectric semiconductor material may be filled. In this way, by the pattern frame placement/peeling method, a thermoelectric conversion material wafer with excellent shape controllability can be easily obtained.

[熱電轉換模組的製造方法] 本發明之熱電轉換模組的製造方法係使用複數個藉由焊錫受理層的形成方法而得到的具有焊錫受理層的前述熱電轉換材料的晶片之熱電轉換模組的製造方法，包含：(xi)將第一電極形成於第一樹脂薄膜上之步驟；(xii)將第二電極形成於第二樹脂薄膜上之步驟；(xiii)將焊錫材料層形成於以前述(xi)之步驟而得到的前述第一電極上之步驟；(xiv)將前述熱電轉換材料的晶片的具有焊錫受理層的一面載置於以前述(xiii)之步驟而得到的前述焊錫材料層上之步驟；(xv)將以前述(xiv)之步驟而載置的前述熱電轉換材料的晶片的具有焊錫受理層的一面，隔著以前述(xiii)之步驟而得到的前述焊錫材料層，來與前述第一電極進行接合之步驟；及，(xvi)將前述(xv)之步驟後的前述熱電轉換材料的晶片的另一面的焊錫受理層，與以前述(xii)之步驟而得到的前述第二電極，以隔著焊錫材料層來進行接合之步驟。 於(xvi)之步驟中，可以在前述熱電轉換材料的晶片的另一面的焊錫受理層上層合有焊錫材料層之態樣，與以(xii)之步驟所得之第二電極接合，也可以在以(xii)之步驟所得的第二電極上層合有焊錫材料層之態樣，與前述熱電轉換材料的晶片的另一面的焊錫受理層接合。[Manufacturing method of thermoelectric conversion module] The method of manufacturing a thermoelectric conversion module of the present invention is a method of manufacturing a thermoelectric conversion module using a plurality of wafers of the aforementioned thermoelectric conversion material having a solder receiving layer obtained by the method of forming a solder receiving layer, including: (xi) The step of forming the first electrode on the first resin film; (xii) the step of forming the second electrode on the second resin film; (xiii) the step of forming the solder material layer on the step (xi) above The step on the aforementioned first electrode; (xiv) the step of placing the solder receiving layer of the wafer of the thermoelectric conversion material on the aforementioned solder material layer obtained in the aforementioned step (xiii); (xv) The side having the solder receiving layer of the wafer of the thermoelectric conversion material placed in the step (xiv) is bonded to the first electrode via the solder material layer obtained in the step (xiii) And, (xvi) the solder receiving layer on the other side of the wafer of the thermoelectric conversion material after the step (xv) and the second electrode obtained in the step (xii) are separated by A layer of solder material is used for the step of joining. In the step (xvi), a solder material layer may be laminated on the solder receiving layer on the other side of the wafer of the thermoelectric conversion material, and it may be joined to the second electrode obtained in the step (xii). The second electrode obtained in the step (xii) with the solder material layer laminated on it is joined to the solder receiving layer on the other side of the wafer of the thermoelectric conversion material.

以下，使用圖式，說明使用複數個藉由本發明之熱電轉換材料的晶片之焊錫受理層的形成方法而得到的具有焊錫受理層的熱電轉換材料的晶片之熱電轉換模組的製造方法。Hereinafter, using the drawings, a method of manufacturing a thermoelectric conversion module using a plurality of thermoelectric conversion material wafers having a solder receiving layer obtained by the method of forming a solder receiving layer of a thermoelectric conversion material wafer of the present invention will be described.

圖3係顯示依照熱電轉換模組的製造方法之步驟的一例之說明圖，該製造方法係使用複數個藉由本發明之對熱電轉換材料的晶片的焊錫受理層的形成方法所得之具有焊錫受理層的熱電轉換材料的晶片，(a)係藉由前述焊錫受理層的形成方法所得之在兩面具有焊錫受理層24a、24b的P型熱電轉換材料的晶片23p及N型熱電轉換材料的晶片23n之剖面圖，(b)係在樹脂薄膜25上形成有電極26及焊錫材料層27後之剖面圖，(c)係顯示在(b)所得之樹脂薄膜25上的電極26上之焊錫材料層27上，載置具有焊錫受理層24a之P型熱電轉換材料的晶片23p及N型熱電轉換材料的晶片23n之態樣的剖面圖，(d)係顯示載置P型熱電轉換材料的晶片23p及N型熱電轉換材料的晶片23n後之態樣的剖面示意圖，(e)係顯示將焊錫材料層27加熱冷卻而接合後之態樣(焊錫材料層27’)，(f)係將在(b)所得之樹脂薄膜25的電極26上之焊錫材料層27與P型熱電轉換材料的晶片23p及N型熱電轉換材料的晶片23n之焊錫受理層24b予以貼合後之剖面圖，(g)係藉由加熱冷卻在(f)所用之焊錫材料層27，而接合具有焊錫受理層24a、24b之P型熱電轉換材料的晶片23p及N型熱電轉換材料的晶片23n與電極26後之剖面圖。FIG. 3 is an explanatory diagram showing an example of the steps of a method of manufacturing a thermoelectric conversion module using a plurality of solder receiving layers obtained by the method for forming a solder receiving layer of a thermoelectric conversion material wafer of the present invention The wafer of thermoelectric conversion material, (a) is obtained by the aforementioned method of forming the solder receiving layer, which is one of the P-type thermoelectric conversion material wafer 23p and the N-type thermoelectric conversion material wafer 23n having solder receiving layers 24a, 24b on both sides The cross-sectional view, (b) is a cross-sectional view after the electrode 26 and the solder material layer 27 are formed on the resin film 25, and (c) is the solder material layer 27 on the electrode 26 on the resin film 25 obtained in (b) Above, a cross-sectional view of the state where the P-type thermoelectric conversion material wafer 23p and the N-type thermoelectric conversion material wafer 23n with the solder receiving layer 24a are placed, (d) shows the P-type thermoelectric conversion material wafer 23p and A schematic cross-sectional view of the state after the wafer 23n of N-type thermoelectric conversion material, (e) shows the state after heating and cooling the solder material layer 27 and joining (the solder material layer 27'), (f) will be in (b) ) A cross-sectional view of the solder material layer 27 on the electrode 26 of the obtained resin film 25 and the P-type thermoelectric conversion material wafer 23p and the N-type thermoelectric conversion material wafer 23n after bonding the solder receiving layer 24b, (g) The solder material layer 27 used in (f) is heated and cooled, and the P-type thermoelectric conversion material wafer 23p having the solder receiving layers 24a and 24b and the N-type thermoelectric conversion material wafer 23n and the electrode 26 are cross-sectional view after joining.

＜電極形成步驟＞ 電極形成步驟係在本發明之熱電轉換模組的製造方法中，例如於(xi)之步驟中，將第一電極形成於第一樹脂薄膜上之步驟，或於(xii)之步驟中，將第二電極形成於第二樹脂薄膜上之步驟，於圖3(b)中，例如在樹脂薄膜25上將金屬層成膜，將彼等加工成指定的圖型，形成電極26之步驟。＜Steps of forming electrodes＞ The electrode forming step is in the method of manufacturing the thermoelectric conversion module of the present invention. For example, in the step (xi), the first electrode is formed on the first resin film, or in the step (xii), the The step of forming the second electrode on the second resin film is shown in FIG. 3(b). For example, a metal layer is formed on the resin film 25 and processed into a specified pattern to form the electrode 26.

(樹脂薄膜) 於本發明之熱電轉換模組的製造方法中，較佳為使用對於熱電轉換材料晶片的電導率之降低、熱傳導率之增加不造成影響的第一樹脂薄膜及第二樹脂薄膜。其中，從彎曲性優異，即使將包含熱電半導體組成物而成之薄膜予以退火處理時，也基板不熱變形，可維持熱電轉換材料晶片之性能，耐熱性及尺寸安定性高之點來看，各自獨立地較佳為聚醯亞胺薄膜、聚醯胺薄膜、聚醚醯亞胺薄膜、聚芳醯胺薄膜、聚醯胺醯亞胺薄膜，再者從通用性高之點來看，特佳為聚醯亞胺薄膜。(Resin film) In the manufacturing method of the thermoelectric conversion module of the present invention, it is preferable to use the first resin film and the second resin film that do not affect the decrease in the electrical conductivity of the thermoelectric conversion material chip and the increase in the thermal conductivity. Among them, from the viewpoint of excellent flexibility, even when a thin film containing a thermoelectric semiconductor composition is annealed, the substrate is not thermally deformed, and the performance of the thermoelectric conversion material wafer can be maintained, and the heat resistance and dimensional stability are high. Each independently is preferably a polyimide film, a polyimide film, a polyetherimide film, a polyaramide film, and a polyimide film. Furthermore, from the viewpoint of high versatility, the characteristics It is preferably a polyimide film.

從彎曲性、耐熱性及尺寸安定性之觀點來看，前述第一樹脂薄膜及第二樹脂薄膜的厚度各自獨立地較佳為1～1000μm，更佳為5～500μm，尤佳為10～100 μm。又，前述第一樹脂薄膜及第二樹脂薄膜係以熱重量分析所測定的5%重量減少溫度較佳為300℃以上，更佳為400℃以上。依據JIS K7133(1999)在200℃測定的加熱尺寸變化率較佳為0.5 %以下，更佳為0.3%以下。依據JIS K7197(2012)測定的平面方向之線膨脹係數為0.1ppm・℃^-1 ～50ppm・℃^-1 ，較佳為0.1ppm・℃^-1 ～30ppm・℃^-1 。From the viewpoint of flexibility, heat resistance, and dimensional stability, the thickness of the first resin film and the second resin film are independently preferably 1 to 1000 μm, more preferably 5 to 500 μm, and particularly preferably 10 to 100 μm. In addition, the 5% weight loss temperature of the first resin film and the second resin film measured by thermogravimetric analysis is preferably 300°C or higher, more preferably 400°C or higher. The heating dimensional change rate measured at 200°C in accordance with JIS K7133 (1999) is preferably 0.5% or less, more preferably 0.3% or less. The coefficient of linear expansion in the plane direction measured in accordance with JIS K7197 (2012) is 0.1 ppm·°C ^-1 to 50 ppm·°C ^-1 , preferably 0.1 ppm·°C ^-1 to 30 ppm·°C ^-1 .

(電極) 作為用於本發明的熱電轉換模組之電極的金屬材料，可舉出銅、金、鎳、鋁、銠、鉑、鉻、鈀、不鏽鋼、鉬或包含此等的任一金屬之合金等。前述電極之層的厚度較佳為10nm～200μm，更佳為30nm～150μm，尤佳為50nm～120μm。若電極之層的厚度為上述範圍內，則電導率高而成為低電阻，得到作為電極的充分強度。(electrode) Examples of the metal material used for the electrode of the thermoelectric conversion module of the present invention include copper, gold, nickel, aluminum, rhodium, platinum, chromium, palladium, stainless steel, molybdenum, or alloys containing any of these metals. The thickness of the aforementioned electrode layer is preferably 10 nm to 200 μm, more preferably 30 nm to 150 μm, and particularly preferably 50 nm to 120 μm. If the thickness of the electrode layer is within the above range, the electrical conductivity is high, the resistance is low, and sufficient strength as an electrode is obtained.

電極之形成係使用前述金屬材料進行。 作為形成電極之方法，可舉出在樹脂薄膜上設置未形成圖型的電極後，藉由以微影法為主體的眾所周知之物理處理或化學處理或併用彼等等，加工成指定的圖型形狀之方法，或藉由網版印刷法、噴墨法等直接形成電極的圖型之方法等。 作為未形成圖型的電極之形成方法，可舉出真空蒸鍍法、濺鍍法、離子鍍法等之PVD(物理氣相成長法)、或熱CVD、原子層蒸鍍(ALD)等之CVD(化學氣相成長法)等之乾式製程、或浸塗法、旋塗法、噴塗法、凹版塗佈法、模塗法、刮刀法等之各種塗佈或電沈積法等之濕式製程、銀鹽法、電鍍法、無電電鍍法、金屬箔之層合等，可按照電極之材料而適宜選擇。 於用於本發明的電極中，從維持熱電性能之觀點來看，要求高的導電性、高的熱傳導性，因此較佳為使用以鍍敷法或真空成膜法所成膜的電極。從可容易地實現高的導電性、高的熱傳導性來看，較佳為真空蒸鍍法、濺鍍法等之真空成膜法，以及電鍍法、無電電鍍法。雖然亦取決於形成圖型的尺寸、尺寸精度之要求，但亦可透過金屬遮罩等之硬遮罩，容易地形成圖型。The formation of the electrode is carried out using the aforementioned metal materials. As a method of forming an electrode, an electrode without a pattern formed on a resin film is provided, and then processed into a specified pattern by a well-known physical treatment or chemical treatment based on the photolithography method, or a combination of them. The method of shape, or the method of directly forming the pattern of the electrode by screen printing method, inkjet method, etc. As a method of forming an electrode that is not patterned, PVD (physical vapor deposition) such as vacuum evaporation, sputtering, and ion plating, or thermal CVD, atomic layer evaporation (ALD), etc. Dry process such as CVD (chemical vapor growth method), or wet process such as dip coating, spin coating, spray coating, gravure coating, die coating, doctor blade method, etc., or electrodeposition method, etc. , Silver salt method, electroplating method, electroless plating method, metal foil lamination, etc., can be appropriately selected according to the electrode material. In the electrode used in the present invention, high electrical conductivity and high thermal conductivity are required from the viewpoint of maintaining thermoelectric performance. Therefore, it is preferable to use an electrode formed by a plating method or a vacuum film forming method. In terms of easily achieving high electrical conductivity and high thermal conductivity, vacuum film forming methods such as a vacuum vapor deposition method and a sputtering method, as well as electroplating methods and electroless plating methods are preferred. Although it also depends on the requirements of the size and dimensional accuracy of the formed pattern, the pattern can also be easily formed through a hard mask such as a metal mask.

前述金屬材料之層的厚度較佳為10nm～200 μm，更佳為30nm～150μm，尤佳為50nm～120μm。若金屬材料之層的厚度為上述範圍內，則電導率高而成為低電阻，得到作為電極的充分強度。The thickness of the aforementioned metal material layer is preferably 10 nm to 200 μm, more preferably 30 nm to 150 μm, and particularly preferably 50 nm to 120 μm. When the thickness of the metal material layer is within the above range, the electrical conductivity is high, the resistance is low, and sufficient strength as an electrode can be obtained.

＜接合材料層形成步驟＞ 接合材料層形成步驟係本發明之熱電轉換模組的製造方法之例如前述(xiii)之步驟，為在第一電極上形成焊錫材料層之步驟。又，例如於前述(xvi)之步驟中所包含者，為在第二電極上形成焊錫材料層之步驟。 具體而言，例如如同圖3(b)所示，在電極26上形成焊錫材料層27之步驟，焊錫材料層係用於接合熱電轉換材料的晶片與電極。於本發明中，可使用後述之焊錫材料，作為焊錫材料層形成在電極上，也可形成在焊錫受理層上。再者，本說明書中所謂導電性，就是指電阻率未達1×10⁶ Ω・m。<Joint Material Layer Formation Step> The joining material layer formation step is the step of (xiii) in the method of manufacturing the thermoelectric conversion module of the present invention, which is a step of forming a solder material layer on the first electrode. Also, for example, what is included in the step (xvi) is a step of forming a solder material layer on the second electrode. Specifically, for example, as shown in FIG. 3(b), a step of forming a solder material layer 27 on the electrode 26, the solder material layer is used to join the wafer and the electrode of the thermoelectric conversion material. In the present invention, the solder material described later may be used as a solder material layer formed on the electrode, or may be formed on the solder receiving layer. Furthermore, the so-called conductivity in this specification means that the resistivity is less than 1×10 ⁶ Ω·m.

作為構成前述焊錫材料層之焊錫材料，只要考慮樹脂薄膜、熱電轉換材料的晶片中所包含的耐熱性樹脂之耐熱溫度等，或導電性、熱傳導性，適宜選擇即可，可舉出Sn、Sn/Pb合金、Sn/Ag合金、Sn/Cu合金、Sn/Sb合金、Sn/In合金、Sn/Zn合金、Sn/In/Bi合金、Sn/In/Bi/Zn合金、Sn/Bi/Pb/Cd合金、Sn/Bi/Pb合金、Sn/Bi/Cd合金、Bi/Pb合金、Sn/Bi/Zn合金、Sn/Bi合金、Sn/Bi/Pb合金、Sn/Pb/Cd合金、Sn/Cd合金等之已知材料。從無鉛及/或無鎘、熔點、導電性、熱傳導性之觀點來看，較佳為如43Sn/57Bi合金、42Sn/58Bi合金、40Sn/56Bi/4Zn合金、48Sn/52In合金、39.8Sn/52In/7Bi/1.2Zn合金之合金。 作為焊錫材料之市售品，可舉出以下者。例如，可使用42Sn/58Bi合金(TAMURA製作所公司製，製品名：SAM10-401-27)、41Sn/58Bi/Ag合金(日本焊錫公司製，製品名：PF141-LT7HO)、96.5Sn3Ag0.5Cu合金(日本焊錫公司製，製品名：PF305-207BTO)等。As the solder material constituting the aforementioned solder material layer, as long as it considers the heat resistance temperature of the resin film, the heat-resistant resin contained in the wafer of the thermoelectric conversion material, etc., or the electrical conductivity and thermal conductivity, it can be selected as appropriate. Examples include Sn and Sn. /Pb alloy, Sn/Ag alloy, Sn/Cu alloy, Sn/Sb alloy, Sn/In alloy, Sn/Zn alloy, Sn/In/Bi alloy, Sn/In/Bi/Zn alloy, Sn/Bi/Pb /Cd alloy, Sn/Bi/Pb alloy, Sn/Bi/Cd alloy, Bi/Pb alloy, Sn/Bi/Zn alloy, Sn/Bi alloy, Sn/Bi/Pb alloy, Sn/Pb/Cd alloy, Sn /Cd alloy and other known materials. From the viewpoints of lead-free and/or cadmium-free, melting point, electrical conductivity, and thermal conductivity, preferably 43Sn/57Bi alloy, 42Sn/58Bi alloy, 40Sn/56Bi/4Zn alloy, 48Sn/52In alloy, 39.8Sn/52In /7Bi/1.2Zn alloy alloy. Examples of commercially available solder materials include the following. For example, 42Sn/58Bi alloy (manufactured by Tamura Manufacturing Co., Ltd., product name: SAM10-401-27), 41Sn/58Bi/Ag alloy (manufactured by Japan Soldering Company, product name: PF141-LT7HO), 96.5Sn3Ag0.5Cu alloy ( Manufactured by Japan Soldering Company, product name: PF305-207BTO) and so on.

焊錫材料層的厚度(加熱冷卻後)較佳為10～200μm，更佳為20～150μm，尤佳為30～130μm，特佳為40～120μm。若焊錫材料層的厚度在該範圍，則容易得到與熱電轉換材料的晶片及電極之密著性。The thickness of the solder material layer (after heating and cooling) is preferably 10 to 200 μm, more preferably 20 to 150 μm, particularly preferably 30 to 130 μm, particularly preferably 40 to 120 μm. If the thickness of the solder material layer is in this range, it is easy to obtain adhesion to the wafer and the electrode of the thermoelectric conversion material.

作為將焊錫材料塗佈於基板上之方法，可舉出模板印刷、網版印刷、分配法等之眾所周知的方法。加熱溫度雖然隨著所用的焊錫材料、樹脂薄膜等而不同，但通常在150～280℃進行3～20分鐘。As a method of applying the solder material on the substrate, well-known methods such as stencil printing, screen printing, and dispensing method can be cited. Although the heating temperature varies with the solder material, resin film, etc. used, it is usually 150 to 280°C for 3 to 20 minutes.

＜熱電轉換材料晶片載置步驟＞ 熱電轉換材料晶片載置步驟係本發明之熱電轉換模組的製造方法之例如前述(xiv)等之步驟，為將藉由前述熱電轉換材料的晶片之製造方法所得的熱電轉換材料的晶片之一面載置於以前述(xiii)等之步驟所得的前述焊錫材料層上之步驟，例如於圖3(c)中，在樹脂薄膜25的電極26上之焊錫材料層27上，使用晶片安裝機(未圖示)的手部28，將具有焊錫受理層24a及24b之P型熱電轉換材料的晶片23p以及具有焊錫受理層24a及24b之N型熱電轉換材料的晶片23n，以各自的焊錫受理層24a之面在焊錫材料層27之上表面且各自在電極26上成為一對之方式載置之步驟(成為載置後(d)的態樣)。 P型熱電轉換材料的晶片、N型熱電轉換材料的晶片之配置係可按照用途，組合同型者彼此，也可例如「・・・NPPN・・・」、「・・・PNPP・・・」等任意地組合。從得到理論上高的熱電性能之觀點來看，較佳為將P型熱電轉換材料的晶片及N型熱電轉換材料的晶片之成對隔著電極複數配置。 作為將熱電轉換材料的晶片載置於焊錫材料層上之方法，並沒有特別的限制，可使用眾所周知之方法。例如，可舉出以前述晶片安裝機等處理熱電轉換材料的晶片1個或複數，以相機等進行對位，進行載置等之方法。 從處理性、載置精度、量產性之觀點來看，熱電轉換材料的晶片較佳為藉由晶片安裝機進行載置。＜Steps for placing thermoelectric conversion material wafers＞ The step of placing the thermoelectric conversion material wafer is the step of (xiv) in the method of manufacturing the thermoelectric conversion module of the present invention, and is to transfer one side of the wafer of the thermoelectric conversion material obtained by the method of manufacturing a wafer of the thermoelectric conversion material. The step of placing on the aforementioned solder material layer obtained by the aforementioned steps (xiii), for example, in FIG. 3(c), on the solder material layer 27 on the electrode 26 of the resin film 25, using a chip mounter ( (Not shown) of the hand 28, the P-type thermoelectric conversion material wafer 23p having the solder receiving layers 24a and 24b and the N-type thermoelectric conversion material wafer 23n having the solder receiving layers 24a and 24b are used with their respective solder receiving layers A step of placing the surface of 24a on the upper surface of the solder material layer 27 and each being a pair on the electrode 26 (the state after placing (d)). The arrangement of P-type thermoelectric conversion material chips and N-type thermoelectric conversion material chips can be combined with each other according to the application. It can also be such as "・・・NPPN・・・", "・・・PNPP・・・", etc. Combine arbitrarily. From the viewpoint of obtaining theoretically high thermoelectric performance, it is preferable to arrange a plurality of pairs of P-type thermoelectric conversion material wafers and N-type thermoelectric conversion material wafers with electrodes interposed therebetween. There is no particular limitation on the method of placing the wafer of thermoelectric conversion material on the solder material layer, and a well-known method can be used. For example, a method of processing one or a plurality of wafers of thermoelectric conversion material with the aforementioned wafer mounter or the like, and positioning and mounting with a camera or the like can be mentioned. From the viewpoints of handling properties, placement accuracy, and mass productivity, the thermoelectric conversion material chip is preferably placed by a chip mounter.

＜接合步驟＞ 接合步驟係本發明之熱電轉換模組的製造方法之例如前述(xv)之步驟，為將以前述(xiv)之步驟所載置的前述熱電轉換材料的晶片之一面隔著以前述(xiii)等之步驟所得的前述焊錫材料層而與前述第一電極接合之步驟，例如於將圖3之(c)的焊錫材料層27加熱到指定的溫度，保持指定的時間保持後，回到室溫之步驟。 又，本發明之熱電轉換模組的製造方法之例如前述(xvi)之步驟，為將以前述(xv)之步驟後之前述熱電轉換材料的晶片的另一面之焊錫受理層與以前述(xii)等之步驟所得的前述第二電極，隔著焊錫材料層進行接合之步驟，例如於圖3(f)中，將(e)中之P型熱電轉換材料的晶片23p上之焊錫受理層24b之面及N型熱電轉換材料的晶片23n上的焊錫受理層24b之面，各自隔著焊錫材料層27，與樹脂薄膜25上的電極26接合之步驟。又，圖3(g)係顯示加熱冷卻(f)的焊錫材料層27後之態樣(焊錫材料層27’)。 接合條件之加熱溫度、保持時間等係如前述。再者，圖3之(e)係使焊錫材料層27回到室溫後之態樣(焊錫材料層27’係因加熱冷卻而固化，厚度減少)。＜Joining procedure＞ The bonding step is, for example, the step (xv) in the method of manufacturing the thermoelectric conversion module of the present invention, which is to place one side of the wafer of the thermoelectric conversion material placed in the step (xiv) with the above (xiii) The step of joining the solder material layer obtained by the steps and the like to the first electrode, for example, is to heat the solder material layer 27 of FIG. 3(c) to a specified temperature, keep it for a specified time, and then return to room temperature.的步。 The steps. In addition, in the method of manufacturing the thermoelectric conversion module of the present invention, for example, the step (xvi) is to combine the solder receiving layer on the other side of the chip of the thermoelectric conversion material after the step (xv) with the solder receiving layer of the chip (xii). The step of joining the aforementioned second electrode obtained in the steps of (e) and the like through the layer of solder material, for example, in FIG. 3(f), the solder receiving layer 24b on the wafer 23p of the P-type thermoelectric conversion material in (e) The step of joining the solder receiving layer 24b on the wafer 23n and the surface of the N-type thermoelectric conversion material wafer 23n to the electrode 26 on the resin film 25 via the solder material layer 27. 3(g) shows the state (solder material layer 27') after heating and cooling the solder material layer 27 of (f). The heating temperature and holding time of the bonding conditions are as described above. Furthermore, Fig. 3(e) shows the state after the solder material layer 27 is returned to room temperature (the solder material layer 27' is solidified by heating and cooling, and the thickness is reduced).

藉由使用複數個藉由本發明之焊錫受理層的形成方法而得到的具有焊錫受理層的前述熱電轉換材料的晶片之熱電轉換模組的製造方法，可製造熱電性能的降低經抑制之熱電轉換模組。 實施例The method for manufacturing a thermoelectric conversion module using a plurality of wafers of the aforementioned thermoelectric conversion material having a solder receiving layer obtained by the method of forming a solder receiving layer of the present invention can produce a thermoelectric conversion module with suppressed degradation of thermoelectric performance group. Example

接著，藉由實施例更詳細地說明本發明，惟本發明完全不受此等之例所限定。Next, the present invention will be explained in more detail with examples, but the present invention is not limited by these examples at all.

實施例、比較例所製作的熱電轉換模組之電阻值的評價、熱電轉換模組之冷卻性能的評價以及熱電轉換材料的晶片與焊錫受理層之接觸電阻值的評價，係用以下之方法進行。 (a)熱電轉換模組之電阻值評價 使用低電阻測定裝置(日置電機公司製，型名：RM3545)，於25℃×50%RH之環境下測定所得之熱電轉換模組之取出電極部間之電阻值。 (b)熱電轉換模組之冷卻性能評價 藉由將使用所得之P型及N型熱電轉換材料的晶片而構成的熱電轉換模組配置於圖4所示之冷卻特性評價單元31的隔熱材38及39之內側的指定位置，進行冷卻特性評價。 具體而言，以相接於熱電轉換模組32的散熱面33側之銅板34成為散熱片35側之方式配置，使用定電壓/定電流直流電源(高砂製作所公司製，型名：KX-100L)，使輸出增大直到熱電轉換模組32的散熱面33側之銅板34的溫度成為85℃為止，使用熱電偶(K型)，測定與吸熱面36側的銅板37之溫度差△T。散熱片35係使用熱阻值8K/W者。The evaluation of the resistance value of the thermoelectric conversion module produced in the Examples and Comparative Examples, the evaluation of the cooling performance of the thermoelectric conversion module, and the evaluation of the contact resistance between the wafer of the thermoelectric conversion material and the solder receiving layer were performed by the following methods . (a) Evaluation of resistance value of thermoelectric conversion module Using a low-resistance measuring device (manufactured by Hioki Electric Co., Ltd., model name: RM3545), the resistance between the lead-out electrodes of the resulting thermoelectric conversion module was measured under an environment of 25°C×50%RH. (b) Cooling performance evaluation of thermoelectric conversion module The thermoelectric conversion module formed by using the obtained P-type and N-type thermoelectric conversion material wafers is arranged at a designated position inside the heat insulating materials 38 and 39 of the cooling characteristic evaluation unit 31 shown in FIG. 4 for cooling. Characteristic evaluation. Specifically, the copper plate 34 connected to the heat dissipation surface 33 side of the thermoelectric conversion module 32 is placed on the heat sink 35 side, and a constant voltage/constant current DC power supply (manufactured by Takasago Manufacturing Co., Ltd., model name: KX-100L) is used. ), the output is increased until the temperature of the copper plate 34 on the heat dissipation surface 33 side of the thermoelectric conversion module 32 reaches 85°C, and the temperature difference ΔT with the copper plate 37 on the heat absorption surface 36 side is measured using a thermocouple (K type). The heat sink 35 uses a thermal resistance value of 8K/W.

(c)接觸電阻值評價 (接觸電阻值測定用試片之製作及對接觸電阻值測定用電極之層合) 製作於P型熱電轉換材料的晶片之上表面及下表面，藉由本發明之焊錫受理層的形成方法所形成之具有焊錫受理層的試片A、B(1.5×1.5mm，厚度：250μm)，及於P型熱電轉換材料的晶片的全部的面上，形成有焊錫受理層的試片C (1.65×1.65mm、厚度：250μm)，層合到接觸電阻值測定用電極。(c) Evaluation of contact resistance (Production of test piece for measurement of contact resistance value and lamination of electrode for measurement of contact resistance value) The test pieces A and B (1.5×1.5mm, thickness: 250μm) with solder receiving layer formed on the upper surface and lower surface of the wafer of P-type thermoelectric conversion material by the solder receiving layer forming method of the present invention, A test piece C (1.65×1.65 mm, thickness: 250 μm) with a solder receiving layer formed on the entire surface of the P-type thermoelectric conversion material wafer was laminated to the electrode for measuring contact resistance.

＜試片A、B及C之製作＞ (i)熱電轉換材料的晶片之製作 於厚度0.7mm的玻璃基板(鈉鈣玻璃)上，將在甲苯中溶解有聚甲基甲基丙烯酸甲酯樹脂(PMMA)(Sigma-Aldrich公司製，商品名：聚甲基丙烯酸甲酯)之固體成分15%的聚甲基甲基丙烯酸甲酯樹脂溶液，藉由旋塗法，以乾燥後的厚度成為3.0μm之方式進行成膜，作為犧牲層。 接著，使用金屬遮罩(印刷圖型：1.65mm×1.65mm，印刷圖型之數：18列×12行，高度：300μm，材質：磁性不鏽鋼)，在犧牲層上，藉由網版印刷法塗佈後述之實施例所調製的塗佈液(P)，於溫度125℃、氬氣環境下乾燥15分鐘，形成厚度為270μm的薄膜。接著，對於所得之薄膜，於氫與氬之混合氣體(氫：氬=3體積%：97體積%)環境下，以加溫速度5K/min進行升溫，在450℃保持1小時，退火處理前述薄膜，使熱電半導體材料的粒子進行結晶成長，得到包含P型鉍碲化物Bi_0.4 Te₃ Sb_1.6 之上下表面各自為1.65mm×1.65mm且厚度為250μm的長方體狀之熱電轉換材料的晶片。 (ii)焊錫受理層的形成 將退火處理後的P型熱電轉換材料的晶片從玻璃基板上剝離，藉由無電電鍍法，在P型熱電轉換材料的晶片的全部之面上設置焊錫受理層[在Ni(厚度：2μm)上層合Au (厚度：30nm)](相當於對應後述比較例1之試片，作為試片C使用於評價)。 可使熱電轉換材料的晶片之一側面對齊而重疊複數片，於經對齊的複數片晶片的一側面能露出之模具中，設置100片的所得之熱電轉換材料的晶片。熱電轉換材料的晶片係僅抛光之厚度部分從模具突出。對於該突出之熱電轉換材料的晶片，進行噴砂處理，而去除各晶片之一面的焊錫受理層。同樣地重複3次，去除全部之側面的焊錫受理層，得到1.5mm×1.5mm、厚度250μm之熱電轉換材料的晶片(此晶片係相當於對應後述實施例2之試片，作為試片B使用於評價)。 同樣地，使用砂紙(號數2000)去除P型熱電轉換材料的晶片的側面之焊錫受理層的全部，得到1.5mm×1.5mm、厚度250μm之熱電轉換材料的晶片(此晶片係相當於對應後述實施例1之試片，作為試片A使用於評價)。<Production of test pieces A, B and C> (i) The production of the thermoelectric conversion material wafer on a glass substrate (soda lime glass) with a thickness of 0.7 mm, and the polymethyl methacrylate resin is dissolved in toluene (PMMA) (manufactured by Sigma-Aldrich, trade name: polymethyl methacrylate) 15% solid content polymethyl methacrylate resin solution, by spin coating method, the thickness after drying becomes 3.0 The film is formed in μm as a sacrificial layer. Next, use a metal mask (printing pattern: 1.65mm×1.65mm, number of printing patterns: 18 columns×12 rows, height: 300μm, material: magnetic stainless steel), on the sacrificial layer, by screen printing The coating liquid (P) prepared in the examples described later was applied, and dried at a temperature of 125° C. in an argon atmosphere for 15 minutes to form a thin film with a thickness of 270 μm. Next, the obtained film is heated at a heating rate of 5K/min under a mixed gas of hydrogen and argon (hydrogen:argon=3vol%:97vol%), kept at 450°C for 1 hour, and annealed as described above Thin film is used to crystallize particles of thermoelectric semiconductor material to obtain _{a wafer containing a rectangular parallelepiped thermoelectric conversion material with a P-type bismuth telluride Bi 0.4} Te ₃ Sb _1.6 whose upper and lower surfaces are 1.65 mm×1.65 mm and a thickness of 250 μm. (ii) Formation of the solder receiving layer The annealed P-type thermoelectric conversion material wafer is peeled from the glass substrate, and the solder receiving layer is provided on the entire surface of the P-type thermoelectric conversion material wafer by electroless plating. [ Au (thickness: 30 nm)] was laminated on Ni (thickness: 2 μm) (corresponding to a test piece corresponding to Comparative Example 1 described later, used as test piece C for evaluation). One side of the wafers of thermoelectric conversion material can be aligned to overlap a plurality of wafers, and 100 wafers of the obtained thermoelectric conversion material are set in a mold in which one side of the aligned plural wafers can be exposed. Only the polished thickness of the wafer of thermoelectric conversion material protrudes from the mold. Sandblasting is performed on the protruding wafers of thermoelectric conversion material to remove the solder receiving layer on one side of each wafer. The same procedure was repeated three times to remove the solder receiving layer on all sides, and a 1.5mm×1.5mm, 250μm thick thermoelectric conversion material wafer was obtained (this wafer is equivalent to the test piece corresponding to Example 2 described later, and is used as test piece B For evaluation). Similarly, use sandpaper (number 2000) to remove all of the solder receiving layer on the side surface of the P-type thermoelectric conversion material wafer to obtain a 1.5mm×1.5mm, 250μm thick thermoelectric conversion material wafer (this wafer is equivalent to the corresponding one described later) The test piece of Example 1 was used as test piece A for evaluation).

＜對接觸電阻值測定用電極之層合＞ 準備貼附有銅箔之聚醯亞胺薄膜基板(宇部EXSYMO公司製，製品名：Upisel N，聚醯亞胺基板，厚度：12.5 μm，銅箔，厚度：12μm)，於該聚醯亞胺薄膜基板之銅箔上，藉由無電電鍍，依序層合鎳層(厚度：9μm)及金層(厚度：40 nm)，製作具有電極之基板。 於基板上之電極上，使用焊膏(日本焊錫公司製，品名：PF141-LT7HO F=10)作為接合材料，藉由網版印刷法形成焊錫材料層。接著，於焊錫材料層上，載置上述所得之P型熱電轉換材料的晶片之焊錫受理層的一面(於試片C亦同樣，不是側面側，而是上下表面之任一面)，在180℃加熱1分鐘後冷卻，而將P型熱電轉換材料的晶片配置於電極上。＜Laminating electrodes for measuring contact resistance value＞ Prepare a polyimide film substrate (manufactured by Ube EXSYMO Co., Ltd., product name: Upisel N, polyimide substrate, thickness: 12.5 μm, copper foil, thickness: 12 μm) on which copper foil is attached. On the copper foil of the thin film substrate, by electroless plating, a nickel layer (thickness: 9μm) and a gold layer (thickness: 40 nm) are sequentially laminated to produce a substrate with electrodes. On the electrodes on the substrate, using solder paste (manufactured by Nippon Soldering Co., Ltd., product name: PF141-LT7HO F=10) as the bonding material, the solder material layer was formed by the screen printing method. Next, on the solder material layer, the side of the solder receiving layer of the wafer of the P-type thermoelectric conversion material obtained above is placed (the same is true for the test piece C, not the side surface, but any one of the upper and lower surfaces) at 180°C After heating for 1 minute and cooling, the P-type thermoelectric conversion material wafer is placed on the electrode.

同樣地，製作於P型熱電轉換材料的晶片之上表面及下表面，藉由網版印刷法直接形成的具有焊錫受理層之試片D(1.5×1.5mm，厚度：250μm)，層合到接觸電阻值測定用電極。Similarly, a test piece D (1.5×1.5mm, thickness: 250μm) with a solder receiving layer formed directly on the upper surface and lower surface of the wafer of P-type thermoelectric conversion material by screen printing is laminated to Electrode for measuring contact resistance.

＜試片D之製作＞ (i)熱電轉換材料的晶片之製作 除了將前述試片A、B及C之製作的(i)所使用之金屬遮罩變更下述之規格以外，與前述試片A、B及C之製作的(i)同樣地，製作P型熱電轉換材料的晶片。 ・金屬遮罩(印刷圖型；1.5mm×1.5mm，印刷圖型之數：18列×12行，高度：300μm，材質：磁性不鏽鋼) (ii)焊錫受理層之形成 於所得之P型熱電轉換材料的晶片上表面，藉由網版印刷法形成銀膏(三之星機帶公司製，製品名：MDotEC264)作為焊錫受理層，在50℃加熱10分鐘。焊錫受理層的厚度係設為10μm(相當於對應後述比較例2之試片，作為試片D使用於評價。惟，為在P型熱電轉換材料的晶片之下表面未形成焊錫受理層之態樣)。＜Production of sample D＞ (i) Fabrication of chips of thermoelectric conversion materials Except that the metal mask used in (i) for the production of the aforementioned test pieces A, B and C was changed to the following specifications, the P type was produced in the same way as (i) for the production of the aforementioned test pieces A, B and C Wafers of thermoelectric conversion materials. ・Metal mask (printing pattern; 1.5mm×1.5mm, number of printing patterns: 18 columns×12 rows, height: 300μm, material: magnetic stainless steel) (ii) Formation of solder receiving layer On the upper surface of the obtained P-type thermoelectric conversion material wafer, a silver paste (manufactured by Mitsuboshi Tape Co., Ltd., product name: MDotEC264) was formed as a solder receiving layer by a screen printing method, and heated at 50°C for 10 minutes. The thickness of the solder receiving layer was set to 10 μm (corresponding to the test piece corresponding to Comparative Example 2 described later, which was used as test piece D for evaluation. However, the solder receiving layer was not formed on the lower surface of the P-type thermoelectric conversion material wafer kind).

＜對接觸電阻值測定用電極之層合＞ 製作與試片A、B及C之製作中所用者相同規格之具有電極的基板，於基板上之電極上，使用焊膏(日本焊錫公司製，品名：PF141-LT7HO F=10)作為接合材料，藉由網版印刷法形成接合材料層。接著，於接合材料層上，以上述所得之P型熱電轉換材料的晶片之焊錫受理層的上表面成為接合面進行載置，在180℃加熱1分鐘後冷卻，而將P型熱電轉換材料的晶片配置於電極上。再者，於所配置的晶片之另一接合面上，亦同樣地層合焊錫受理層。＜Laminating electrodes for measuring contact resistance value＞ Make a substrate with electrodes of the same specifications as those used in the production of test pieces A, B, and C. On the electrodes on the substrate, use solder paste (manufactured by Nippon Soldering Co., Ltd., product name: PF141-LT7HO F=10) as the bonding material , The bonding material layer is formed by the screen printing method. Next, on the bonding material layer, the upper surface of the solder receiving layer of the P-type thermoelectric conversion material wafer obtained above is placed as the bonding surface, heated at 180°C for 1 minute and then cooled, and the P-type thermoelectric conversion material The wafer is arranged on the electrode. Furthermore, the solder receiving layer is also laminated on the other bonding surface of the arranged chip in the same manner.

(接觸電阻值測定) 圖5係用於說明上述所得的試片A之P型熱電轉換材料的晶片與焊錫受理層之界面的接觸電阻值之測定方法之概略圖。構成試片A41的P型熱電轉換材料的晶片41t之下表面的焊錫受理層41d，係隔著接合材料層42而接合至接觸電阻值測定用電極43，於25℃50%RH之環境下，使用低電阻測定裝置44(日置公司製，型名：RM3545)，以4端子法測定焊錫受理層41u之上表面中央部與接觸電阻值測定用電極43之上表面的未設置試片A41之區域的中央部之間的電阻值，將其當作P型熱電轉換材料的晶片41t與接合電極間之接觸電阻值。測定係對於試片B、試片C、試片D，亦同樣地實施。表1中顯示結果。(Measurement of contact resistance) 5 is a schematic diagram for explaining the method of measuring the contact resistance value of the interface between the wafer of the P-type thermoelectric conversion material of the test piece A and the solder receiving layer obtained above. The solder receiving layer 41d on the lower surface of the wafer 41t of the P-type thermoelectric conversion material constituting the test piece A41 is joined to the contact resistance measurement electrode 43 via the joining material layer 42 under an environment of 25°C and 50%RH. Using a low-resistance measuring device 44 (manufactured by Hioki, model name: RM3545), the area on the upper surface of the solder receiving layer 41u and the upper surface of the contact resistance measurement electrode 43 where the test piece A41 is not provided was measured by the 4-terminal method The resistance value between the center parts of the P-type thermoelectric conversion material was regarded as the contact resistance value between the wafer 41t and the bonding electrode. The measurement system is similarly performed for test piece B, test piece C, and test piece D. The results are shown in Table 1.

(實施例1) (1)熱電半導體組成物之製作 (熱電半導體粒子之製作) 使用行星式球磨機(FRITSCH日本公司製Premium line P-7)，將鉍-碲系熱電半導體材料之P型鉍碲化物Bi_0.4 Te₃ Sb_1.6 (高純度化學研究所製，粒徑：180μm)在氮氣環境下粉碎，製作平均粒徑2.0μm的熱電半導體粒子T1。關於粉碎所得之熱電半導體粒子，藉由雷射繞射式粒度分析裝置(Malvern公司製Mastersizer 3000)進行粒度分布測定。 又，與上述同樣地粉碎鉍-碲系熱電半導體材料之N型鉍碲化物Bi₂ Te₃ (高純度化學研究所製，粒徑：180μm)，製作平均粒徑2.8μm的熱電半導體粒子T2。(Example 1) (1) Production of thermoelectric semiconductor composition (production of thermoelectric semiconductor particles) Using a planetary ball mill (Premium line P-7 manufactured by FRITSCH Japan), the P-type bismuth tellurium of the bismuth-tellurium thermoelectric semiconductor material The compound Bi _0.4 Te ₃ Sb _1.6 (manufactured by the High Purity Chemical Laboratory, particle size: 180 μm) was pulverized in a nitrogen atmosphere to produce thermoelectric semiconductor particles T1 with an average particle size of 2.0 μm. Regarding the pulverized thermoelectric semiconductor particles, the particle size distribution was measured with a laser diffraction particle size analyzer (Mastersizer 3000 manufactured by Malvern Corporation). _{In addition, the N-type bismuth telluride Bi 2} Te ₃ (manufactured by High Purity Chemical Laboratory, particle size: 180 μm), which is a bismuth-tellurium-based thermoelectric semiconductor material, was crushed in the same manner as described above to produce thermoelectric semiconductor particles T2 with an average particle diameter of 2.8 μm.

(熱電半導體組成物的塗佈液之調製) ・塗佈液(P) 調製塗佈液(P)，其包含將所得之P型鉍碲化物Bi_0.4 Te₃ Sb_1.6 的粒子T1 82.5質量%、作為耐熱性樹脂的聚醯亞胺前驅物之聚醯胺酸(宇部興產公司製，U-清漆A，溶劑：N-甲基吡咯啶酮，固體成分濃度：18質量%)3.2質量%(固體成分)及作為離子液體的1-丁基吡啶鎓溴化物14.3質量%予以混合分散而成之熱電半導體組成物。 ・塗佈液(N) 調製塗佈液(N)，其包含將所得之N型鉍碲化物Bi₂ Te₃ 的粒子T2 91.6質量%、作為耐熱性樹脂聚醯亞胺前驅物聚醯胺酸(宇部興產公司製，U-清漆A，溶劑：N-甲基吡咯啶酮、固體成分濃度：18質量%)3.6質量%(固體成分)及作為離子液體的1-丁基吡啶鎓溴化物4.8質量%予以混合分散而成之熱電半導體組成物。 (2)熱電轉換材料的薄膜之形成 於厚度0.7mm的玻璃基板(鈉鈣玻璃)上，將在甲苯中溶解有聚甲基甲基丙烯酸甲酯樹脂(PMMA)(Sigma-Aldrich公司製，商品名：聚甲基丙烯酸甲酯)之固體成分15%的聚甲基甲基丙烯酸甲酯樹脂溶液，藉由旋塗法，以乾燥後的厚度成為3.0μm之方式進行成膜，作為犧牲層。 接著，透過金屬遮罩，在犧牲層上，藉由網版印刷法塗佈上述(1)所調製之塗佈液(P)，於溫度125℃、氬氣環境下乾燥15分鐘，形成厚度為270μm的薄膜。接著，對於所得之薄膜，於氫與氬之混合氣體(氫：氬=3體積%：97體積%)環境下，以加溫速度5K/min進行升溫，在450℃保持1小時，退火處理前述薄膜，使熱電半導體材料的粒子進行結晶成長，得到包含P型鉍碲化物Bi_0.4 Te₃ Sb_1.6 之上下表面各自為1.65mm×1.65mm且厚度為250μm的長方體狀之熱電轉換材料的晶片。 又，除了變更為上述(1)所調製的塗佈液(N)，於溫度125℃、氬氣環境下乾燥7分鐘以外，同樣地得到包含N型鉍碲化物Bi₂ Te₃ 之上下表面各自為1.65mm×1.65mm且厚度為250μm的長方體狀之熱電轉換材料的晶片。(Preparation of coating liquid for thermoelectric semiconductor composition) ・Coating liquid (P) Prepare coating liquid (P), which contains the obtained P-type bismuth telluride Bi _0.4 Te ₃ Sb _1.6 particles T1 82.5 mass%, Polyamide acid (manufactured by Ube Industries Co., Ltd., U-varnish A, solvent: N-methylpyrrolidone, solid content concentration: 18% by mass) as a polyimide precursor of a heat-resistant resin, 3.2% by mass ( Solid content) and 14.3% by mass of 1-butylpyridinium bromide as an ionic liquid are mixed and dispersed in a thermoelectric semiconductor composition.・Coating solution (N) Prepare coating solution (N), which contains _{91.6% by mass of the obtained N-type bismuth telluride Bi 2} Te ₃ particles T2 91.6% by mass, as a heat-resistant resin polyimide precursor polyamide acid (Manufactured by Ube Industries Co., Ltd., U-varnish A, solvent: N-methylpyrrolidone, solid content concentration: 18% by mass) 3.6% by mass (solid content) and 1-butylpyridinium bromide as an ionic liquid 4.8% by mass mixed and dispersed thermoelectric semiconductor composition. (2) A thin film of thermoelectric conversion material is formed on a glass substrate (soda lime glass) with a thickness of 0.7 mm, and polymethyl methacrylate resin (PMMA) (manufactured by Sigma-Aldrich, a product manufactured by Sigma-Aldrich) is dissolved in toluene. Name: polymethyl methacrylate) 15% solid content polymethyl methacrylate resin solution, by spin coating method, the thickness after drying is formed into a film of 3.0μm, as a sacrificial layer. Next, through the metal mask, on the sacrificial layer, the coating solution (P) prepared in (1) above was coated by screen printing, and dried at a temperature of 125°C in an argon atmosphere for 15 minutes to form a thickness of 270μm film. Next, the obtained film is heated at a heating rate of 5K/min under a mixed gas of hydrogen and argon (hydrogen:argon=3vol%:97vol%), kept at 450°C for 1 hour, and annealed as described above Thin film is used to crystallize particles of thermoelectric semiconductor material to obtain _{a wafer containing a rectangular parallelepiped thermoelectric conversion material with a P-type bismuth telluride Bi 0.4} Te ₃ Sb _1.6 whose upper and lower surfaces are 1.65 mm×1.65 mm and a thickness of 250 μm. Also, except for changing to the coating solution (N) prepared in (1) above, and drying at 125°C for 7 minutes in an argon atmosphere, the upper and lower surfaces _{containing N-type bismuth telluride Bi 2} Te _{3 were similarly obtained.} It is a rectangular parallelepiped thermoelectric conversion material wafer with a thickness of 1.65 mm×1.65 mm and a thickness of 250 μm.

(焊錫受理層的形成) 將退火處理後之各自的熱電轉換材料的晶片從玻璃基板上剝離，藉由無電電鍍法，在各自的熱電轉換材料的晶片的全部之面設置焊錫受理層[在Ni(厚度：2μm)上層合Au(厚度：30nm)]。 接著，以晶片成為1.5mm×1.5mm之尺寸的方式，使用機械抛光法，亦即使用砂紙(號數2000)，去除P型及N型熱電轉換材料的晶片的側面之焊錫受理層，得到僅在上下表面具有焊錫受理層之P型及N型熱電轉換材料的晶片。再者，為了完全去除焊錫受理層，亦包含抛光側面的壁之一部分。(Formation of solder receiving layer) After the annealing treatment, the respective thermoelectric conversion material wafers are peeled from the glass substrate, and by electroless plating, a solder receiving layer is provided on the entire surface of the respective thermoelectric conversion material wafers [Laminated on Ni (thickness: 2μm) Au (thickness: 30 nm)]. Next, using a mechanical polishing method such that the wafer has a size of 1.5mm×1.5mm, that is, using sandpaper (number 2000), the solder receiving layer on the side surface of the wafer of P-type and N-type thermoelectric conversion materials is removed to obtain only A wafer of P-type and N-type thermoelectric conversion materials with solder receiving layers on the upper and lower surfaces. Furthermore, in order to completely remove the solder receiving layer, a part of the wall on the side surface is polished.

(熱電轉換模組之製作) 使用所得之僅在上下表面具有焊錫受理層之P型及N型熱電轉換材料的晶片，如以下地製作由P型及N型熱電轉換材料的晶片各自18組所成之π型的熱電轉換模組。 首先，準備貼附有銅箔之聚醯亞胺薄膜基板(宇部EXSYMO公司製，製品名：Upisel N，聚醯亞胺基板，厚度：12.5μm，銅箔，厚度：12μm)，於該聚醯亞胺薄膜基板之銅箔上，藉由無電電鍍，依序層合鎳層(厚度：9μm)及金層(厚度：40nm)，製作具有電極之基板，於該電極上，使用焊膏(日本焊錫公司製，品名：PF141-LT7HO F=10)作為焊錫材料，網版印刷焊錫材料層(厚度：30μm)。接著，於焊錫材料層上，載置上述所得之P型及N型熱電轉換材料的晶片各自之焊錫受理層的一面，在180℃加熱1分鐘後冷卻，而將P型及N型熱電轉換材料的晶片各自配置於電極上。 再者，於P型及N型熱電轉換材料的晶片各自之焊錫受理層的另一面上，印刷前述焊膏(厚度：30μm)作為焊錫材料層，使與上部電極薄膜(與下部電極薄膜貼合時，以得到π型的熱電轉換模組之方式圖型配置有電極之電極薄膜；基板、電極的材料、厚度等係與下部電極相同)的電極貼合，使用真空層壓機(Nikko-Materials公司製，型名：V-130)，於0.2 hPa下在180℃加熱6分鐘、壓接，得到由P型及N型熱電轉換材料的晶片各自18組所成之π型的熱電轉換模組。 進行所得之熱電轉換模組的電阻值之評價及熱電轉換模組的冷卻性能之評價。表1中顯示結果。(Production of thermoelectric conversion module) Using the obtained P-type and N-type thermoelectric conversion material wafers with solder-receiving layers only on the upper and lower surfaces, a π-type thermoelectric conversion mold composed of 18 sets of P-type and N-type thermoelectric conversion material wafers was produced as follows: group. First, prepare a polyimide film substrate (manufactured by Ube EXSYMO Co., Ltd., product name: Upisel N, polyimide substrate, thickness: 12.5 μm, copper foil, thickness: 12 μm) on which copper foil is attached. On the copper foil of the imine film substrate, by electroless plating, a nickel layer (thickness: 9μm) and a gold layer (thickness: 40nm) were sequentially laminated to make a substrate with electrodes. On the electrodes, solder paste (Japan Manufactured by a soldering company, product name: PF141-LT7HO F=10) As the solder material, the solder material layer (thickness: 30 μm) was screen printed. Next, on the solder material layer, the above-obtained P-type and N-type thermoelectric conversion materials are placed on one side of the solder receiving layer of each of the wafers, heated at 180°C for 1 minute and then cooled, and the P-type and N-type thermoelectric conversion materials The wafers are each arranged on the electrode. In addition, the solder paste (thickness: 30μm) was printed on the other side of the solder receiving layer of each of the P-type and N-type thermoelectric conversion material wafers as a solder material layer to be bonded to the upper electrode film (and the lower electrode film) When the π-type thermoelectric conversion module is obtained, the electrode film with the electrode is patterned; the substrate and the material and thickness of the electrode are the same as the lower electrode). The electrode is attached using a vacuum laminator (Nikko-Materials Manufactured by the company, model name: V-130), heated at 180°C for 6 minutes at 0.2 hPa and crimped to obtain a π-type thermoelectric conversion module composed of 18 groups of P-type and N-type thermoelectric conversion material wafers. . The resistance value of the obtained thermoelectric conversion module and the cooling performance of the thermoelectric conversion module were evaluated. The results are shown in Table 1.

(實施例2) 除了於實施例1中，使用噴砂裝置(不二製作所公司製，型名：SC-3)，使用平均粒徑20μm的抛光劑(不二製作所公司製，氧化鋁含有率99%以上，型號：WA-600)，於0.1Mpa之壓力下去除(噴砂處理；與試片B同樣)側面的焊錫受理層以外，與實施例1同樣地製作熱電轉換模組。 進行所得之熱電轉換模組的電阻值之評價及熱電轉換模組的冷卻性能之評價。表1中顯示結果。(Example 2) Except for Example 1, a sandblasting device (manufactured by Fuji Manufacturing Co., model name: SC-3) was used, and a polishing agent with an average particle size of 20 μm (manufactured by Fuji Manufacturing Co., Ltd., with an alumina content of 99% or more, model: WA-600), except that the solder receiving layer on the side surface was removed under a pressure of 0.1Mpa (sandblasting; the same as test piece B), a thermoelectric conversion module was produced in the same manner as in Example 1. The resistance value of the obtained thermoelectric conversion module and the cooling performance of the thermoelectric conversion module were evaluated. The results are shown in Table 1.

(比較例1) 除了於實施例1中，不去除P型及N型熱電轉換材料的晶片側面之焊錫受理層以外，與實施例1同樣地製作熱電轉換模組。 進行所得之熱電轉換模組的電阻值之評價及熱電轉換模組的冷卻性能之評價。表1中顯示結果。(Comparative example 1) In Example 1, a thermoelectric conversion module was produced in the same manner as in Example 1, except that the solder receiving layer on the side of the wafer of the P-type and N-type thermoelectric conversion materials was not removed. The resistance value of the obtained thermoelectric conversion module and the cooling performance of the thermoelectric conversion module were evaluated. The results are shown in Table 1.

(比較例2) 除了於實施例1中，以網版印刷法僅在P型及N型熱電轉換材料的晶片上下表面形成焊錫受理層(與試片D相同規格的焊錫受理層，厚度10μm)以外，與實施例1同樣地製作熱電轉換模組。(Comparative example 2) Except that in Example 1, only the upper and lower surfaces of the P-type and N-type thermoelectric conversion material wafers were formed on the upper and lower surfaces of the solder-receiving layer (the solder-receiving layer of the same specification as the test piece D, thickness 10μm) by the screen printing method. 1 In the same way, a thermoelectric conversion module was produced.

進行所得之熱電轉換模組的電阻值之評價及熱電轉換模組的冷卻性能之評價。表1中顯示結果。

The resistance value of the obtained thermoelectric conversion module and the cooling performance of the thermoelectric conversion module were evaluated. The results are shown in Table 1.

使用熱電轉換材料的晶片所製作之實施例1及2之熱電轉換模組，該熱電轉換材料的晶片係在熱電轉換材料的晶片之上下表面具有焊錫受理層，在側面藉由本發明之焊錫受理層的形成方法去除焊錫受理層而不具有焊錫受理層者，相較於使用在熱電轉換材料的晶片的全部之面上具有焊錫受理層之熱電轉換材料的晶片所製作之比較例1之熱電轉換模組，可知得到較高的溫度差，熱電性能提升。 又，同樣地，相較於使用雖然在熱電轉換材料的晶片的側面不具有焊錫受理層，但僅在熱電轉換材料的晶片之上下表面，藉由網版印刷法形成有焊錫受理層之熱電轉換材料的晶片所製作之比較例2之熱電轉換模組，可知得到較高的溫度差，熱電性能提升。 由以上可知，藉由本發明之對熱電轉換材料的晶片的焊錫受理層的形成方法，可抑制熱電性能之降低。 產業上的利用可能性The thermoelectric conversion modules of Examples 1 and 2 produced by using a chip of thermoelectric conversion material. The chip of thermoelectric conversion material has a solder receiving layer on the upper and lower surfaces of the chip of thermoelectric conversion material, and the solder receiving layer of the present invention is provided on the side The formation method of removing the solder receiving layer without the solder receiving layer is compared with the thermoelectric conversion model of Comparative Example 1 produced by using the thermoelectric conversion material wafer with the solder receiving layer on all surfaces of the thermoelectric conversion material wafer Group, it can be seen that a higher temperature difference is obtained, and the thermoelectric performance is improved. Also, similarly, compared to the use of thermoelectric conversion material that does not have a solder receiving layer on the side surface of the wafer of thermoelectric conversion material, only the upper and lower surfaces of the wafer of thermoelectric conversion material have a solder receiving layer formed by the screen printing method. The thermoelectric conversion module of Comparative Example 2 made of a chip made of a material shows that a higher temperature difference is obtained, and the thermoelectric performance is improved. From the above, it can be seen that the method for forming the solder receiving layer for the thermoelectric conversion material wafer of the present invention can suppress the degradation of the thermoelectric performance. Industrial possibilities

依照本發明之對熱電轉換材料的晶片的焊錫受理層的形成方法，及使用藉由其形成方法所得的晶片之熱電轉換模組的製造方法，藉由在熱電轉換材料的晶片之焊錫受理層之中，去除前述熱電轉換材料的晶片的側面上所形成的部分之全部或一部分，由於可使熱電轉換材料的晶片之熱電半導體組成物適當地導通，結果可消除熱電性能降低等之問題。同時，可期待製造步驟內的良率之提高。 茲認為藉由上述之對熱電轉換材料的晶片的焊錫受理層的形成方法所得之使用熱電轉換材料的晶片之熱電轉換模組，係可適用將來自工廠或廢棄物燃燒爐、水泥燃燒爐等之各種燃燒爐的排熱、汽車的燃燒氣體排熱及電子機器的排熱，進行電轉換之發電用途。作為冷卻用途，於電子機器之領域中，例如可適用於智慧型手機、各種電腦等所用之CPU(中央處理單元，Central Processing Unit)，以及CMOS(互補金屬氧化物半導體影像感測器，Complementary Metal Oxide Semiconductor Image Sensor)、CCD(電荷耦合裝置，Charge Coupled Device)等之影像感測器，更且MEMS(微電子機械系統，Micro Electro Mechanical Systems)、其他的受光元件等之各種感測器的溫度控制等。According to the method for forming the solder receiving layer of the chip of thermoelectric conversion material and the method of manufacturing the thermoelectric conversion module using the chip obtained by the method of the present invention, the solder receiving layer of the chip of the thermoelectric conversion material In this, removing all or a part of the part formed on the side surface of the thermoelectric conversion material wafer can properly conduct the thermoelectric semiconductor composition of the thermoelectric conversion material wafer, and as a result, problems such as degradation of thermoelectric performance can be eliminated. At the same time, the yield rate in the manufacturing steps can be expected to increase. It is considered that the thermoelectric conversion module of the chip using thermoelectric conversion material obtained by the above-mentioned method of forming the solder receiving layer of the thermoelectric conversion material chip can be applied to the heat from the factory, waste burning furnace, cement burning furnace, etc. The exhaust heat of various combustion furnaces, the exhaust heat of the combustion gas of automobiles and the exhaust heat of electronic equipment, and the use of electricity conversion. As a cooling purpose, in the field of electronic equipment, for example, it can be applied to CPU (Central Processing Unit) used in smart phones, various computers, and CMOS (Complementary Metal). Oxide Semiconductor Image Sensor), CCD (Charge Coupled Device) and other image sensors, and MEMS (Micro Electro Mechanical Systems), other light-receiving components and other sensors Control etc.

1p:P型熱電轉換材料的晶片 1n:N型熱電轉換材料的晶片 2a:上表面(P型或N型熱電轉換材料的晶片) 2b:下表面(P型或N型熱電轉換材料的晶片) 2c:側面(P型或N型熱電轉換材料的晶片) 3:焊錫受理層 4p:P型熱電轉換材料的晶片(僅在上下表面具有焊錫受理層) 4n:N型熱電轉換材料的晶片(僅在上下表面具有焊錫受理層) 11:基板 12:圖型框 12’:不鏽鋼 13:開口部 13d:開口部深度(圖型框厚) 13s:開口 14a:N型熱電轉換材料層 14b:P型熱電轉換材料層 14n:N型熱電轉換材料的晶片 14p:P型熱電轉換材料的晶片 23n:N型熱電轉換材料的晶片 23p:P型熱電轉換材料的晶片 24a:焊錫受理層 24b:焊錫受理層 25:樹脂薄膜 26:電極 27:焊錫材料層 27’:焊錫材料層 28:手部 31:冷卻特性評價單元 32:熱電轉換模組 33:散熱面 34:銅板 35:散熱片 36:吸熱面 37:銅板 38:隔熱材 39:隔熱材 41:試片A 41t:P型熱電轉換材料的晶片 41u:焊錫受理層 41d:焊錫受理層 42:接合材料層(焊錫材料層) 43:接觸電阻值測定用電極 44:低電阻測定裝置1p: P-type thermoelectric conversion material wafer 1n: N-type thermoelectric conversion material wafer 2a: Upper surface (P-type or N-type thermoelectric conversion material wafer) 2b: Lower surface (P-type or N-type thermoelectric conversion material wafer) 2c: Side (P-type or N-type thermoelectric conversion material wafer) 3: Solder acceptance layer 4p: P-type thermoelectric conversion material wafer (only with solder receiving layer on the upper and lower surfaces) 4n: N-type thermoelectric conversion material wafer (only with solder receiving layer on the upper and lower surfaces) 11: substrate 12: picture frame 12’: Stainless steel 13: Opening 13d: Depth of the opening (thickness of the pattern frame) 13s: opening 14a: N-type thermoelectric conversion material layer 14b: P-type thermoelectric conversion material layer 14n: N-type thermoelectric conversion material wafer 14p: P-type thermoelectric conversion material wafer 23n: N-type thermoelectric conversion material wafer 23p: P-type thermoelectric conversion material wafer 24a: Solder acceptance layer 24b: Solder acceptance layer 25: Resin film 26: Electrode 27: Solder material layer 27’: Solder material layer 28: Hands 31: Cooling characteristic evaluation unit 32: Thermoelectric conversion module 33: cooling surface 34: copper plate 35: heat sink 36: Endothermic surface 37: copper plate 38: Insulation material 39: Insulation material 41: Test piece A 41t: P-type thermoelectric conversion material wafer 41u: Solder acceptance layer 41d: Solder acceptance layer 42: Joining material layer (solder material layer) 43: Electrode for measuring contact resistance 44: Low resistance measuring device

[圖1]係用於說明本發明之對熱電轉換材料的晶片的焊錫受理層的形成方法之實施態樣的一例之剖面構成圖。 [圖2]係依步驟順序顯示圖型框配置/剝離法之熱電轉換材料的晶片之製造方法的一例之說明圖。 [圖3]係顯示依照熱電轉換模組的製造方法之步驟的一例之說明圖，該製造方法係使用複數個藉由本發明之對熱電轉換材料的晶片的焊錫受理層的形成方法所得之具有焊錫受理層的熱電轉換材料的晶片。 [圖4]係用於說明本發明之實施例所製作的熱電轉換模組之冷卻特性評價單元之剖面概略圖。 [圖5]係用於說明本發明之實施例所製作的試片之熱電轉換材料的晶片與焊錫受理層之界面的接觸電阻值之測定方法之概略圖。[Fig. 1] Fig. 1 is a cross-sectional configuration diagram for explaining an example of an embodiment of the method of forming a solder receiving layer of a thermoelectric conversion material wafer of the present invention. [FIG. 2] An explanatory diagram showing an example of a manufacturing method of a thermoelectric conversion material wafer by the pattern frame placement/peeling method in the order of steps. [FIG. 3] An explanatory diagram showing an example of the steps in accordance with the manufacturing method of the thermoelectric conversion module using a plurality of solders obtained by the method of forming the solder receiving layer of the thermoelectric conversion material chip of the present invention Accept the layer of thermoelectric conversion material wafer. [Fig. 4] is a schematic cross-sectional view for explaining the cooling characteristic evaluation unit of the thermoelectric conversion module manufactured by the embodiment of the present invention. Fig. 5 is a schematic diagram for explaining the method of measuring the contact resistance value of the interface between the wafer of the thermoelectric conversion material and the solder receiving layer of the test piece produced in the embodiment of the present invention.

1p:P型熱電轉換材料的晶片 1p: P-type thermoelectric conversion material wafer

1n:N型熱電轉換材料的晶片 1n: N-type thermoelectric conversion material wafer

2a:上表面(P型或N型熱電轉換材料的晶片) 2a: Upper surface (P-type or N-type thermoelectric conversion material wafer)

2b:下表面(P型或N型熱電轉換材料的晶片) 2b: Lower surface (P-type or N-type thermoelectric conversion material wafer)

2c:側面(P型或N型熱電轉換材料的晶片) 2c: Side (P-type or N-type thermoelectric conversion material wafer)

3:焊錫受理層 3: Solder acceptance layer

4p:P型熱電轉換材料的晶片(僅在上下表面具有焊錫受理層) 4p: P-type thermoelectric conversion material wafer (only with solder receiving layer on the upper and lower surfaces)

4n:N型熱電轉換材料的晶片(僅在上下表面具有焊錫受理層) 4n: N-type thermoelectric conversion material wafer (only with solder receiving layer on the upper and lower surfaces)

Claims (9)

一種焊錫受理層的形成方法，其係將焊錫受理層形成於具有上表面、下表面及側面的熱電轉換材料的晶片上之方法，前述熱電轉換材料係包含熱電半導體組成物而成， 包含下述步驟(A)及步驟(B)， (A)將前述焊錫受理層形成於前述熱電轉換材料的晶片的全部的面上之步驟； (B)將以前述(A)之步驟而得到的形成於前述熱電轉換材料的晶片的側面上的焊錫受理層之全部或一部分予以去除之步驟。A method for forming a solder receiving layer, which is a method of forming a solder receiving layer on a wafer having a thermoelectric conversion material having an upper surface, a lower surface and a side surface, the thermoelectric conversion material comprising a thermoelectric semiconductor composition, Including the following steps (A) and (B), (A) A step of forming the solder receiving layer on the entire surface of the wafer of the thermoelectric conversion material; (B) A step of removing all or part of the solder receiving layer formed on the side surface of the wafer of the thermoelectric conversion material obtained in the step (A). 如請求項1之焊錫受理層的形成方法，其中，以無電電鍍法、電鍍法或真空成膜法來進行前述焊錫受理層的形成。The method for forming a solder receiving layer of claim 1, wherein the formation of the solder receiving layer is performed by an electroless plating method, an electroplating method, or a vacuum film forming method. 如請求項1或2之焊錫受理層的形成方法，其中，以機械拋光法、化學拋光法及電解拋光法的表面拋光法中的至少1種來進行前述焊錫受理層的去除。The method for forming a solder receiving layer according to claim 1 or 2, wherein the removal of the solder receiving layer is performed by at least one of a surface polishing method of a mechanical polishing method, a chemical polishing method, and an electrolytic polishing method. 如請求項1~3中任一項之焊錫受理層的形成方法，其中，前述熱電轉換材料的晶片的厚度為100 nm~1000μm。The method for forming a solder receiving layer according to any one of claims 1 to 3, wherein the thickness of the wafer of the thermoelectric conversion material is 100 nm to 1000 μm. 如請求項1~4中任一項之焊錫受理層的形成方法，其中，前述熱電半導體組成物包含熱電半導體材料，且該熱電半導體材料為鉍-碲系熱電半導體材料、碲化物系熱電半導體材料、銻-碲系熱電半導體材料或鉍硒化物系熱電半導體材料。The method for forming a solder receiving layer according to any one of claims 1 to 4, wherein the thermoelectric semiconductor composition includes a thermoelectric semiconductor material, and the thermoelectric semiconductor material is a bismuth-tellurium-based thermoelectric semiconductor material or a telluride-based thermoelectric semiconductor material , Antimony-tellurium series thermoelectric semiconductor materials or bismuth selenide series thermoelectric semiconductor materials. 如請求項1~5中任一項之焊錫受理層的形成方法，其中，前述熱電半導體組成物更包含耐熱性樹脂。The method for forming a solder receiving layer according to any one of claims 1 to 5, wherein the thermoelectric semiconductor composition further includes a heat-resistant resin. 如請求項1~6中任一項之焊錫受理層的形成方法，其中，前述耐熱性樹脂為聚醯亞胺樹脂、聚醯胺樹脂、聚醯胺醯亞胺樹脂或環氧樹脂。The method for forming a solder receiving layer according to any one of claims 1 to 6, wherein the heat-resistant resin is polyimide resin, polyimide resin, polyimide resin, or epoxy resin. 如請求項1~7中任一項之焊錫受理層的形成方法，其中，前述熱電半導體組成物更包含離子液體及/或無機離子性化合物。The method for forming a solder receiving layer according to any one of claims 1 to 7, wherein the thermoelectric semiconductor composition further includes an ionic liquid and/or an inorganic ionic compound. 一種熱電轉換模組的製造方法，其係使用複數個藉由請求項1~8中任一項之焊錫受理層的形成方法而得到的具有焊錫受理層的前述熱電轉換材料的晶片的熱電轉換模組的製造方法， 包含下述步驟(xi)至步驟(xvi)， (xi)將第一電極形成於第一樹脂薄膜上之步驟； (xii)將第二電極形成於第二樹脂薄膜上之步驟； (xiii)將焊錫材料層形成於以前述(xi)之步驟而得到的前述第一電極上之步驟； (xiv)將前述熱電轉換材料的晶片的具有焊錫受理層的一面載置於以前述(xiii)之步驟而得到的前述焊錫材料層上之步驟； (xv)將以前述(xiv)之步驟而載置的前述熱電轉換材料的晶片的具有焊錫受理層的一面，隔著以前述(xiii)之步驟而得到的前述焊錫材料層，來與前述第一電極進行接合之步驟； (xvi)將前述(xv)之步驟後的前述熱電轉換材料的晶片的另一面的焊錫受理層，與以前述(xii)之步驟而得到的前述第二電極，以隔著焊錫材料層來進行接合之步驟。A method of manufacturing a thermoelectric conversion module using a plurality of thermoelectric conversion modules of the aforementioned thermoelectric conversion material wafer having a solder receiving layer obtained by the method for forming a solder receiving layer in any one of claims 1 to 8 The manufacturing method of the group, Including the following steps (xi) to step (xvi), (xi) the step of forming the first electrode on the first resin film; (xii) The step of forming the second electrode on the second resin film; (xiii) a step of forming a layer of solder material on the first electrode obtained in the step (xi); (xiv) the step of placing the solder receiving layer of the wafer of the thermoelectric conversion material on the solder material layer obtained in the step (xiii); (xv) The side having the solder receiving layer of the wafer of the thermoelectric conversion material placed in the step (xiv) is separated from the solder material layer obtained in the step (xiii) and the second A step of electrode bonding; (xvi) The solder receiving layer on the other side of the wafer of the thermoelectric conversion material after the step (xv) and the second electrode obtained in the step (xii) are carried out via the solder material layer. The step of joining.

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