JP2020035818A - Thermoelectric conversion element and method of manufacturing the same - Google Patents
Thermoelectric conversion element and method of manufacturing the same Download PDFInfo
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- JP2020035818A JP2020035818A JP2018159285A JP2018159285A JP2020035818A JP 2020035818 A JP2020035818 A JP 2020035818A JP 2018159285 A JP2018159285 A JP 2018159285A JP 2018159285 A JP2018159285 A JP 2018159285A JP 2020035818 A JP2020035818 A JP 2020035818A
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Abstract
Description
本発明は、熱電変換素子及びその製造方法に関する。 The present invention relates to a thermoelectric conversion element and a method for manufacturing the same.
従来から、エネルギーの有効利用手段の一つとして、ゼーベック効果やペルチェ効果などの熱電効果を有する熱電変換モジュールにより、熱エネルギーと電気エネルギーとを直接相互変換するようにした装置がある。
この中で、前記熱電変換素子として、いわゆるπ型の熱電変換素子の使用が知られている。π型は、通常、互いに離間するー対の電極を基板上に設け、例えば、―方の電極の上にＰ型熱電素子を、他方の電極の上にＮ型熱電素子を、同じく互いに離間して設け、両方の熱電素子の上面を対向する基板の電極に接続することで構成されている。
2. Description of the Related Art Conventionally, as one of means for effectively using energy, there is a device in which heat energy and electric energy are directly mutually converted by a thermoelectric conversion module having a thermoelectric effect such as a Seebeck effect or a Peltier effect.
Among them, use of a so-called π-type thermoelectric conversion element is known as the thermoelectric conversion element. In the π type, usually, a pair of electrodes which are separated from each other are provided on a substrate, and, for example, a P type thermoelectric element is placed on a negative electrode, an N type thermoelectric element is placed on the other electrode, and similarly separated from each other. And the upper surfaces of both thermoelectric elements are connected to the electrodes of the opposing substrate.
近年、熱電変換素子の屈曲性向上、薄型化、高集積化を含む熱電性能の向上等の要求がある。特許文献１では、熱電変換素子に用いる基板として、ポリイミド等の樹脂基板が耐熱性及び屈曲性の観点から使用されている。また、熱電素子層としては、薄膜化による薄型化の観点も含め、液状又はペースト状の低粘度の熱電半導体組成物を用い、スクリーン印刷法等により直接熱電素子層のパターンを形成する方法が開示されている。 In recent years, there has been a demand for improvement in thermoelectric performance including improvement in flexibility, thinness, and high integration of thermoelectric conversion elements. In Patent Document 1, as a substrate used for a thermoelectric conversion element, a resin substrate such as polyimide is used from the viewpoint of heat resistance and flexibility. Also disclosed is a method in which a liquid or paste-like low-viscosity thermoelectric semiconductor composition is used as a thermoelectric element layer and a pattern of the thermoelectric element layer is directly formed by a screen printing method or the like, including a viewpoint of thinning by thinning. Have been.
しかしながら、特許文献１のように、熱電半導体材料、耐熱性樹脂等からなる低粘度の熱電半導体組成物を、スクリーン印刷法等で電極上に熱電素子を直接パターン層として形成する方法では、得られた熱電素子層の形状制御性が十分ではなく、電極界面において熱電素子層の端部に滲みが発生したり、また、熱電素子層の形状が崩れたり等、所望の形状に制御することができず、例えば、前述したπ型熱電変換素子を構成する場合には、得られた熱電素子層の上面と対向基板上の電極面とで、十分な電気的及び物理的接合性が得られない場合がある。この場合、熱抵抗等が増大する等、熱電素子層が本来有する熱電性能を十分引き出すことができなくなり、所定の発電性能又は冷却性能等を得るために、Ｐ型熱電素子層−Ｎ型熱電素子層の対の数を増加させる必要がある。さらに、熱電変換素子の高集積化に際しては、複数の各Ｐ型熱電素子層−Ｎ型熱電素子層対の抵抗値のばらつきが大きくなったり、隣接する熱電素子層同士が接触してしまう場合がある。 However, a method of forming a thermoelectric element as a pattern layer directly on an electrode by a screen printing method or the like using a low-viscosity thermoelectric semiconductor composition composed of a thermoelectric semiconductor material, a heat-resistant resin, or the like, as in Patent Document 1, is obtained. The shape controllability of the thermoelectric element layer is not sufficient, and bleeding occurs at the end of the thermoelectric element layer at the electrode interface, and the shape of the thermoelectric element layer can be controlled to a desired shape such as collapsed. For example, when the above-described π-type thermoelectric conversion element is configured, when sufficient electrical and physical bonding properties cannot be obtained between the upper surface of the obtained thermoelectric element layer and the electrode surface on the counter substrate. There is. In this case, the thermoelectric element layer cannot sufficiently draw out its inherent thermoelectric performance such as an increase in thermal resistance and the like. In order to obtain a predetermined power generation performance or cooling performance, a P-type thermoelectric element layer-N-type thermoelectric element The number of layer pairs needs to be increased. Furthermore, when the thermoelectric conversion elements are highly integrated, the variation in the resistance value of each of the plurality of P-type thermoelectric element layers-N-type thermoelectric element layer pairs may increase, or adjacent thermoelectric element layers may come into contact with each other. is there.
本発明は、上記を鑑み、形状制御性が優れた熱電素子層を有する高集積化が可能な熱電変換素子及びその製造方法を提供することを課題とする。 In view of the above, an object of the present invention is to provide a thermoelectric conversion element having a thermoelectric element layer excellent in shape controllability and capable of high integration, and a method for manufacturing the same.
本発明者らは、上記課題を解決すべく鋭意検討を重ねた結果、基板の電極上に離間した開口部を複数有するパターン層において、パターン層を樹脂を含む層とし、前記開口部に熱電半導体材料を含む熱電半導体組成物からなるＰ型熱電素子層及びＮ型熱電素子層を備える構成とすることにより、形状制御性が優れた熱電素子層を有する高集積化が可能な熱電変換素子、及びその製造方法を見出し、本発明を完成させた。
すなわち、本発明は、以下の（１）〜（８）を提供するものである。
（１）電極を有する基板と、離間した開口部を複数有するパターン層と、前記離間した開口部内に存在するＰ型熱電素子層及びＮ型熱電素子層と、を含む熱電変換素子であって、前記パターン層が樹脂を含む層であり、前記Ｐ型熱電素子層及びＮ型熱電素子層が熱電半導体材料を含む熱電半導体組成物からなる、熱電変換素子。
（２）前記パターン層を構成する樹脂が、ポリイミド樹脂、ポリアミド樹脂、ポリエーテルイミド樹脂、ポリアラミドフィルム、又はポリアミドイミド樹脂である、上記（１）に記載の熱電変換素子。
（３）前記基板が、ポリイミドフィルム、ポリアミドフィルム、ポリエーテルイミドフィルム、ポリアラミドフィルム、又はポリアミドイミドフィルムである、上記（１）に記載の熱電変換素子。
（４）前記熱電半導体材料が、ビスマス−テルル系熱電半導体材料、テルライド系熱電半導体材料、アンチモン−テルル系熱電半導体材料、又はビスマスセレナイド系熱電半導体材料である、上記（１）〜（３）のいずれかに記載の熱電変換素子。
（５）前記熱電半導体組成物が、さらに、耐熱性樹脂、並びにイオン液体及び／又は無機イオン性化合物を含む、上記（１）〜（４）のいずれかに記載の熱電変換素子。
（６）前記耐熱性樹脂が、ポリイミド樹脂、ポリアミド樹脂、ポリアミドイミド樹脂、又はエポキシ樹脂である、上記（５）に記載の熱電変換素子。
（７）前記開口部の形状が、不定形状、多面体状、円錐台状、楕円錐台状、円柱状、及び楕円柱状からなる群より選択される１種以上の形状である、上記（１）に記載の熱電変換素子。
（８）電極を有する基板と、離間した開口部を複数有するパターン層と、前記離間した開口部内にＰ型熱電素子層及びＮ型熱電素子層と、を含む熱電変換素子において、前記パターン層が樹脂を含む層であり、前記Ｐ型熱電素子層及びＮ型熱電素子層が熱電半導体材料を含む熱電半導体組成物からなる、熱電変換素子の製造方法であって、前記電極上に離間した開口部を有するパターン層を形成する工程、前記離間した開口部にＰ型熱電半導体材料を含む熱電半導体組成物及びＮ型熱電半導体材料を含む熱電半導体組成物をそれぞれ充填する工程、前記離間した開口部に充填された、前記Ｐ型熱電半導体材料を含む熱電半導体組成物及び前記Ｎ型熱電半導体材料を含む熱電半導体組成物を乾燥し、Ｐ型熱電素子層及びＮ型熱電素子層を得る工程、並びに得られたＰ型熱電素子層及びＮ型熱電素子層をアニール処理する工程を含む、熱電変換素子の製造方法。
The present inventors have conducted intensive studies in order to solve the above-mentioned problems, and as a result, in a pattern layer having a plurality of openings separated from each other on an electrode of a substrate, the pattern layer is a layer containing a resin, and a thermoelectric semiconductor is provided in the openings. A thermoelectric conversion element capable of high integration having a thermoelectric element layer with excellent shape controllability by having a configuration including a P-type thermoelectric element layer and an N-type thermoelectric element layer made of a thermoelectric semiconductor composition containing a material, and The present inventors have found a manufacturing method and completed the present invention.
That is, the present invention provides the following (1) to (8).
(1) A thermoelectric conversion element including a substrate having electrodes, a pattern layer having a plurality of spaced openings, and a P-type thermoelectric element layer and an N-type thermoelectric element layer present in the spaced openings, The thermoelectric conversion element, wherein the pattern layer is a layer containing a resin, and the P-type thermoelectric element layer and the N-type thermoelectric element layer are made of a thermoelectric semiconductor composition containing a thermoelectric semiconductor material.
(2) The thermoelectric conversion element according to the above (1), wherein the resin constituting the pattern layer is a polyimide resin, a polyamide resin, a polyetherimide resin, a polyaramid film, or a polyamideimide resin.
(3) The thermoelectric conversion element according to (1), wherein the substrate is a polyimide film, a polyamide film, a polyetherimide film, a polyaramid film, or a polyamideimide film.
(4) The above (1) to (3), wherein the thermoelectric semiconductor material is a bismuth-tellurium-based thermoelectric semiconductor material, a telluride-based thermoelectric semiconductor material, an antimony-tellurium-based thermoelectric semiconductor material, or a bismuth selenide-based thermoelectric semiconductor material. The thermoelectric conversion element according to any one of the above.
(5) The thermoelectric conversion element according to any one of (1) to (4), wherein the thermoelectric semiconductor composition further includes a heat-resistant resin, and an ionic liquid and / or an inorganic ionic compound.
(6) The thermoelectric conversion element according to (5), wherein the heat-resistant resin is a polyimide resin, a polyamide resin, a polyamide-imide resin, or an epoxy resin.
(7) The above-mentioned (1), wherein the shape of the opening is at least one selected from the group consisting of an irregular shape, a polyhedral shape, a truncated cone, a truncated elliptical cone, a column, and an elliptic column. 3. The thermoelectric conversion element according to item 1.
(8) A thermoelectric conversion element including a substrate having electrodes, a pattern layer having a plurality of spaced openings, and a P-type thermoelectric element layer and an N-type thermoelectric element layer in the spaced openings. A method for producing a thermoelectric conversion element, wherein the P-type thermoelectric element layer and the N-type thermoelectric element layer are made of a thermoelectric semiconductor composition containing a thermoelectric semiconductor material, wherein the openings are separated from each other on the electrode. Forming a pattern layer having: a step of filling a thermoelectric semiconductor composition containing a P-type thermoelectric semiconductor material and a thermoelectric semiconductor composition containing an N-type thermoelectric semiconductor material into the spaced openings, respectively; The filled thermoelectric semiconductor composition containing the P-type thermoelectric semiconductor material and the thermoelectric semiconductor composition containing the N-type thermoelectric semiconductor material are dried to obtain a P-type thermoelectric element layer and an N-type thermoelectric element layer. The P-type thermoelectric element layer and N-type thermoelectric element layer obtained as well, including the step of annealing method for producing a thermoelectric conversion element.
本発明によれば、形状制御性が優れた熱電素子層を有する高集積化が可能な熱電変換素子及びその製造方法を提供することができる。 According to the present invention, it is possible to provide a thermoelectric conversion element having a thermoelectric element layer having excellent shape controllability and capable of being highly integrated, and a method for manufacturing the same.
［熱電変換素子］
本発明の熱電変換素子は、電極を有する基板と、離間した開口部を複数有するパターン層と、前記離間した開口部内に存在するＰ型熱電素子層及びＮ型熱電素子層と、を含む熱電変換素子であって、前記パターン層が樹脂を含む層であり、前記Ｐ型熱電素子層及びＮ型熱電素子層が熱電半導体材料を含む熱電半導体組成物からなることを特徴としている。
本発明の熱電変換素子は、樹脂を含む層からなるパターン層の離間した開口部に、Ｐ型熱電素子層及びＮ型熱電素子層を備えることにより、Ｐ型熱電素子層及びＮ型熱電素子層のいずれの形状も、パターン層の開口部の形状がそのまま反映されるため、得られる両熱電素子層の形状制御性が優れたものになる。このため、熱電変換素子を構成する電極面との接合性等が向上し、熱抵抗等の増大による熱電性能の低下が抑制され、熱電素子層が本来有する熱電性能が発現される。結果的に、所定の熱電性能を得るための熱電素子層の数を減少させることができ、製造コストの削減に繋がる。同時に、冷却にあっては低消費電力化に、また発電にあっては、高出力化に繋がる。さらに、π型の熱電変換素子の集積化に際しては、複数の各Ｐ型熱電素子層−Ｎ型熱電素子層対の抵抗値のばらつきが小さくなり、隣接する熱電素子層同士が接触してしまうこともないことから、高集積化が可能となる。
なお、本明細書において、「開口部」は、後述するように、パターン層全体の領域の内側の領域に複数離間して設けられ、各開口（基板の電極上のパターン層を上面側から見た場合）の平面形状をパターン層の厚さ（深さ）方向に、電極面まで延在し、例えば、開口の平面形状が、長方形である場合、パターン層の形成又は加工方法等により調整できるが、開口部の形状は、通常、略直方体状となる。また、同様に、例えば、開口の平面形状が、円である場合、開口部の形状は、通常、略円柱状となる。
[Thermoelectric conversion element]
A thermoelectric conversion element according to the present invention includes a substrate having electrodes, a pattern layer having a plurality of spaced openings, and a P-type thermoelectric element layer and an N-type thermoelectric element layer present in the separated openings. In the element, the pattern layer is a layer containing a resin, and the P-type thermoelectric element layer and the N-type thermoelectric element layer are made of a thermoelectric semiconductor composition containing a thermoelectric semiconductor material.
The thermoelectric conversion element of the present invention is provided with a P-type thermoelectric element layer and an N-type thermoelectric element layer in a separated opening of a pattern layer made of a layer containing a resin, thereby providing a P-type thermoelectric element layer and an N-type thermoelectric element layer. In any case, the shape of the opening of the pattern layer is directly reflected, so that the shape controllability of the obtained thermoelectric element layers is excellent. For this reason, the bondability with the electrode surface constituting the thermoelectric conversion element is improved, the decrease in thermoelectric performance due to an increase in thermal resistance and the like is suppressed, and the thermoelectric performance inherent to the thermoelectric element layer is exhibited. As a result, the number of thermoelectric element layers for obtaining predetermined thermoelectric performance can be reduced, which leads to a reduction in manufacturing cost. At the same time, cooling leads to lower power consumption, and power generation leads to higher output. Furthermore, when the π-type thermoelectric conversion elements are integrated, the variation in the resistance value of each of the plurality of P-type thermoelectric element layers-N-type thermoelectric element layer pairs is reduced, and adjacent thermoelectric element layers may come into contact with each other. Since there is no such device, high integration is possible.
In this specification, as will be described later, an “opening” is provided in a region inside a region of the entire pattern layer at a plurality of intervals, and each opening (the pattern layer on the electrode of the substrate is viewed from the upper surface side). Is extended to the electrode surface in the thickness (depth) direction of the pattern layer. For example, when the planar shape of the opening is rectangular, it can be adjusted by forming or processing the pattern layer. However, the shape of the opening is generally a substantially rectangular parallelepiped. Similarly, for example, when the plane shape of the opening is a circle, the shape of the opening is usually substantially cylindrical.
図１は、本発明の熱電変換素子（π型熱電変換素子）の一例を説明するための断面構成図である。熱電変換素子１は、基板２ａの電極３ａ上に樹脂を含む層からなるパターン層４の開口５ｓの開口部５に備えたＮ型熱電素子層６ａ及びＰ型熱電素子層６ｂを有し、さらに、Ｎ型熱電素子層６ａ及びＰ型熱電素子層６ｂの上面に、基板２ｂ上に電極３ｂを有する対向電極基板を備える。 FIG. 1 is a cross-sectional configuration diagram for explaining an example of the thermoelectric conversion element (π-type thermoelectric conversion element) of the present invention. The thermoelectric conversion element 1 has an N-type thermoelectric element layer 6a and a P-type thermoelectric element layer 6b provided on an opening 5s of an opening 5s of a pattern layer 4 formed of a layer containing resin on an electrode 3a of a substrate 2a. On the upper surface of the N-type thermoelectric element layer 6a and the P-type thermoelectric element layer 6b, a counter electrode substrate having an electrode 3b on a substrate 2b is provided.
＜パターン層＞
本発明の熱電変換素子は、基板の電極上にパターン層を含み、該パターン層は樹脂を含み、かつ所定の離間した開口部を有する。
<Pattern layer>
The thermoelectric conversion element of the present invention includes a pattern layer on an electrode of a substrate, the pattern layer includes a resin, and has a predetermined spaced opening.
図２は、本発明の熱電変換素子を構成するパターン層の一例を説明するための平面図である（電極部、断面図は図示せず）。パターン層４は、樹脂を含む層からなる所定の離間した、開口５ｓを有する開口部５を含む。
パターン層内に含まれる前記開口及び開口部の配置、個数及び寸法は、開口部間の距離等含め、特に制限されず、熱電素子層の形状及び配置に応じて適宜調整される。
前記開口部の形状は、特に制限されず、所望の形状を用いることができる。好ましくは、不定形状、多面体状、円錐台状、楕円錐台状、円柱状、及び楕円柱状からなる群より選択される１種以上の形状である。多面体状としては、立方体状、直方体状、角錐台状の形状が挙げられる。形成又は加工が容易であることから、立方体状、直方体状、角錐台状及び円柱状がより好ましい。この中で、電極形状、熱電素子層の形状、熱電性能の観点から、直方体状、立方体状であることがさらに好ましい。
図２においては、開口５ｓは正方形であり、開口部５は略立方体状(図示せず)であり、合計４×４個の開口及び開口部を有する。
FIG. 2 is a plan view for explaining an example of a pattern layer constituting the thermoelectric conversion element of the present invention (electrode portions, sectional views are not shown). The pattern layer 4 includes a predetermined spaced opening 5 having a resin-containing layer and having an opening 5s.
The arrangement, the number, and the size of the openings and the openings included in the pattern layer are not particularly limited, including the distance between the openings, and are appropriately adjusted according to the shape and the arrangement of the thermoelectric element layer.
The shape of the opening is not particularly limited, and a desired shape can be used. Preferably, it is at least one shape selected from the group consisting of an irregular shape, a polyhedral shape, a truncated cone, a truncated elliptical cone, a column, and an elliptic column. Examples of the polyhedral shape include a cubic shape, a rectangular parallelepiped shape, and a truncated pyramid shape. A cubic shape, a rectangular parallelepiped shape, a truncated pyramid shape, and a columnar shape are more preferable because of easy formation or processing. Among them, from the viewpoints of the electrode shape, the shape of the thermoelectric element layer, and the thermoelectric performance, the shape is more preferably a rectangular parallelepiped or a cube.
In FIG. 2, the opening 5s is square, and the opening 5 is substantially cubic (not shown), and has a total of 4 × 4 openings and openings.
パターン層に含まれる樹脂としては、例えば、ポリフェニレンエーテル樹脂、ポリスルホン樹脂、ポリエーテルスルホン樹脂、ポリフェニレンスルフィド樹脂、ポリイミド樹脂、ポリアミド樹脂、ポリエーテルイミド樹脂、ポリアラミドフィルム、エポキシ樹脂、又はポリアミドイミド樹脂等が挙げられる。
この中で、耐熱性（特に、形状安定性）及び加工性の観点から、ポリイミド樹脂、ポリアミド樹脂、ポリエーテルイミド樹脂、ポリアラミドフィルム、又はポリアミドイミド樹脂が好ましい。さらに好ましくは、ポリイミド樹脂、ポリアミド樹脂である。
Examples of the resin contained in the pattern layer include, for example, polyphenylene ether resin, polysulfone resin, polyethersulfone resin, polyphenylene sulfide resin, polyimide resin, polyamide resin, polyetherimide resin, polyaramid film, epoxy resin, polyamideimide resin, and the like. Is mentioned.
Among these, a polyimide resin, a polyamide resin, a polyetherimide resin, a polyaramid film, or a polyamideimide resin is preferable from the viewpoint of heat resistance (particularly, shape stability) and workability. More preferably, they are a polyimide resin and a polyamide resin.
また、パターン層が簡便に形成しやすい観点から、上記樹脂が主成分となる感光性樹脂組成物を用いることができる。感光性樹脂組成物を用いることにより、後述する簡便なプロセスで、離間した開口部を有するパターン層が得られる。
市販の感光性樹脂組成物として、感光性ポリイミド（旭化成社製、ＡＭ−２７０；アルカリ現像ポジ型）、感光性ポリイミド（旭化成社製、Ｉ−８１００；溶剤現像ネガ型）等が挙げられる。
In addition, from the viewpoint of easily forming a pattern layer, a photosensitive resin composition containing the above resin as a main component can be used. By using the photosensitive resin composition, a pattern layer having separated openings can be obtained by a simple process described later.
Examples of commercially available photosensitive resin compositions include photosensitive polyimide (manufactured by Asahi Kasei Corporation, AM-270; alkali developing positive type), photosensitive polyimide (manufactured by Asahi Kasei Corporation, I-8100; solvent developing negative type), and the like.
パターン層には、その他の成分が含まれていてもよい。その他の成分としては、着色剤、難燃剤、可塑剤、滑剤、フィラー、紫外線吸収剤、耐候安定剤、防錆剤、消泡材、濡れ性調整剤等が挙げられる。 The pattern layer may contain other components. Other components include a colorant, a flame retardant, a plasticizer, a lubricant, a filler, an ultraviolet absorber, a weather stabilizer, a rust inhibitor, a defoamer, a wetting agent, and the like.
パターン層の厚さは、熱電素子層の厚さにより適宜調整される。好ましくは１００ｎｍ〜１０００μｍ、より好ましくは１〜６００μｍ、さらに好ましくは１０〜４００μｍ、特に好ましくは、１０〜３００μｍである。 The thickness of the pattern layer is appropriately adjusted according to the thickness of the thermoelectric element layer. It is preferably from 100 nm to 1000 μm, more preferably from 1 to 600 μm, further preferably from 10 to 400 μm, particularly preferably from 10 to 300 μm.
パターン層の形成方法としては、樹脂として感光性樹脂組成物を用いる場合では、フォトリソグラフィー法を主体とした公知の方法を用いることができる。
具体的には、基板の電極上に、ポジ型又はネガ型の感光性樹脂組成物を塗布し、所定の開口のパターンを有するフォトマスクを準備し、露光、現像により、感光性樹脂のパターン層を形成する。ポジ型の場合は、露光部を、例えば、アルカリ等により現像し溶解除去する。また、ネガ型の場合は、未露光部を、例えば、溶剤等により現像し溶解除去する。以上のように、基板の電極上にパターン層を加工する方法等が挙げられる。なお、ポジ型の場合は露光部が溶解するため、現像後の断面形状は曲面を有し、基板の電極面に対する側面の傾斜角度が基板の電極面から離れるにしたがい連続的に小さくなる形状を得ることができる。ネガ型の場合は、ポジ型とは逆に未露光部が現像時に溶解するため、現像後の断面形状が矩形、または、台形に近い形状を得ることができる。これらポジ型、ネガ型の選択は、所望の開口部の形状に合わせて選択することができる。
また、樹脂として、感光性を有しない樹脂組成物を用いる場合でも、フォトリソグラフィー法を主体とした公知の方法を用いることができる。具体的には、基板の電極上に、前記樹脂を塗布し、さらに、フォトレジスト等を塗布し、所定の開口のパターンを有するフォトマスクを準備し、露光、現像により、フォトレジストでパターンを形成し、その後、ウェットエッチング又は酸素プラズマ、反応性イオン等によるドライエッチング等により前記樹脂を溶解又は除去させ、その後、残ったフォトレジストを剥離することで、基板の電極にパターン層を加工する方法等が挙げられる。
前記樹脂の形成方法としては、基板の電極上にディップコーティング法、スピンコーティング法、スプレーコーティング法、グラビアコーティング法、ダイコーティング法、ドクターブレード法等の各種コーティング法が挙げられる。
When a photosensitive resin composition is used as the resin, a known method mainly using a photolithography method can be used as a method for forming the pattern layer.
Specifically, a positive or negative photosensitive resin composition is applied on the electrode of the substrate, and a photomask having a predetermined opening pattern is prepared, and exposed and developed to form a pattern layer of the photosensitive resin. To form In the case of a positive type, the exposed portion is developed and dissolved and removed with, for example, an alkali or the like. In the case of a negative type, the unexposed portion is developed and dissolved and removed with, for example, a solvent or the like. As described above, a method of processing a pattern layer on an electrode of a substrate and the like can be given. In the case of the positive type, since the exposed portion dissolves, the cross-sectional shape after development has a curved surface, and the inclination angle of the side surface with respect to the electrode surface of the substrate continuously decreases as the distance from the electrode surface of the substrate increases. Obtainable. In the case of the negative type, the unexposed portion dissolves during development, contrary to the positive type, so that the cross-sectional shape after development can be a rectangle or a shape close to a trapezoid. The selection between the positive type and the negative type can be made according to the desired shape of the opening.
Further, even when a resin composition having no photosensitivity is used as the resin, a known method mainly using a photolithography method can be used. Specifically, on the electrode of the substrate, the resin is applied, and further, a photoresist or the like is applied, a photomask having a pattern of a predetermined opening is prepared, and a pattern is formed with the photoresist by exposure and development. Then, the resin is dissolved or removed by wet etching or dry etching with oxygen plasma, reactive ions, or the like, and then, by removing the remaining photoresist, a method of processing the pattern layer on the electrode of the substrate, or the like. Is mentioned.
Examples of the method of forming the resin include various coating methods such as a dip coating method, a spin coating method, a spray coating method, a gravure coating method, a die coating method, and a doctor blade method on an electrode of a substrate.
開口部を有するパターン層の他の形成方法としては、レーザー加工法で樹脂を含む層をパターン加工する方法が挙げられる。
具体的には、基板の電極上に、前記樹脂を含む層を塗布し、得られた樹脂を含む層にレーザーを照射して、所定のパターンを直接形成する。パターンを形成するレーザーは固体レーザー、ガスレーザーおよび半導体レーザー等を用いることができる。高出力でランニングコストが低い固体レーザーは好ましく用いることができる。固体レーザーとしては、ＹＡＧやＹＶＯ４結晶からなるレーザーを好ましく用いることができ、ＮｄをドープしたＹＡＧ結晶からなるレーザーの第三光調波である３５４ｎｍ光のレーザーやＮｄをドープしたＹＶＯ４結晶からなるレーザーの第三光調波である３５５ｎｍ光のレーザーが好ましく用いられる。
レーザーは、連続発振でもパルス発振でも用いることができるが、樹脂を含む層が加熱されると熱ダメージによる樹脂を含む層の分解や炭化不良が発生することがある。樹脂を含む層に熱ダメージを与えないためには、パルス発振レーザーが好ましい。パルス幅はより短い方が樹脂を含む層に与える熱ダメージが少ないので好ましく、ナノ秒からピコ秒のパルス幅であるレーザーが好ましい。
As another method for forming a pattern layer having an opening, there is a method in which a layer containing a resin is patterned by a laser processing method.
Specifically, a layer containing the resin is applied on the electrode of the substrate, and the obtained layer containing the resin is irradiated with a laser to directly form a predetermined pattern. As a laser for forming a pattern, a solid laser, a gas laser, a semiconductor laser, or the like can be used. A solid-state laser with high output and low running cost can be preferably used. As the solid-state laser, a laser composed of YAG or YVO 4 crystal can be preferably used, and a laser of 354 nm light, which is the third optical harmonic of the laser composed of Nd-doped YAG crystal, or a Nd-doped YVO 4 crystal can be used. The laser of 355 nm light which is the third optical harmonic of the laser is preferably used.
The laser can be used in either continuous oscillation or pulse oscillation. However, when the layer containing the resin is heated, decomposition or poor carbonization of the layer containing the resin due to thermal damage may occur. In order not to cause thermal damage to the layer containing the resin, a pulsed laser is preferable. A shorter pulse width is preferable because thermal damage to the resin-containing layer is small, and a laser having a pulse width of nanosecond to picosecond is preferable.
（基板）
本発明の熱電変換素子において、基板として、熱電素子層の電気伝導率の低下、熱伝導率の増加に影響を及ぼさない樹脂フィルムを用いる。なかでも、屈曲性に優れ、熱電半導体組成物からなる熱電素子層（薄膜）をアニール処理した場合でも、基板が熱変形することなく、熱電素子層の性能を維持することができ、耐熱性及び寸法安定性が高いという点から、ポリイミドフィルム、ポリアミドフィルム、ポリエーテルイミドフィルム、ポリアラミドフィルム、又はポリアミドイミドフィルムが好ましく、さらに、汎用性が高いという点から、ポリイミドフィルムが特に好ましい。
(substrate)
In the thermoelectric conversion element of the present invention, a resin film that does not affect the decrease in the electrical conductivity of the thermoelectric element layer and the increase in the thermal conductivity is used as the substrate. Above all, even when the thermoelectric element layer (thin film) made of a thermoelectric semiconductor composition is excellent in flexibility and is subjected to annealing treatment, the performance of the thermoelectric element layer can be maintained without thermal deformation of the substrate, and heat resistance and From the viewpoint of high dimensional stability, a polyimide film, a polyamide film, a polyetherimide film, a polyaramid film, or a polyamideimide film is preferable, and from the viewpoint of high versatility, a polyimide film is particularly preferable.
前記樹脂フィルムの厚さは、屈曲性、耐熱性及び寸法安定性の観点から、１〜１０００μｍが好ましく、５〜５００μｍがより好ましく、１０〜１００μｍがさらに好ましい。
また、上記樹脂フィルムは、熱重量分析で測定される５％重量減少温度が３００℃以上であることが好ましく、４００℃以上であることがより好ましい。ＪＩＳ Ｋ７１３３（１９９９）に準拠して２００℃で測定した加熱寸法変化率が０．５％以下であることが好ましく、０．３％以下であることがより好ましい。ＪＩＳ Ｋ７１９７（２０１２）に準拠して測定した平面方向の線膨脹係数が０．１ｐｐｍ・℃−１〜５０ｐｐｍ・℃−１であり、０．１ｐｐｍ・℃−１〜３０ｐｐｍ・℃−１であることがより好ましい。
From the viewpoints of flexibility, heat resistance and dimensional stability, the thickness of the resin film is preferably from 1 to 1000 μm, more preferably from 5 to 500 μm, and still more preferably from 10 to 100 μm.
Further, the resin film preferably has a 5% weight loss temperature measured by thermogravimetric analysis of 300 ° C. or higher, more preferably 400 ° C. or higher. The heating dimensional change measured at 200 ° C. in accordance with JIS K7133 (1999) is preferably 0.5% or less, more preferably 0.3% or less. JIS K7197 (2012) linear expansion coefficient in the planar direction was measured in accordance with is 0.1ppm · ℃ -1 ~50ppm · ℃ -1 , it is 0.1ppm · ℃ -1 ~30ppm · ℃ -1 Is more preferred.
（電極）
本発明に用いる熱電変換素子の電極の金属材料としては、銅、金、ニッケル、アルミニウム、ロジウム、白金、クロム、パラジウム、ステンレス鋼、モリブデン又はこれらのいずれかの金属を含む合金等が挙げられる。
前記電極の層の厚さは、好ましくは１０ｎｍ〜２００μｍ、より好ましくは３０ｎｍ〜１５０μｍ、さらに好ましくは５０ｎｍ〜１２０μｍである。電極の層の厚さが、上記範囲内であれば、電気伝導率が高く低抵抗となり、電極として十分な強度が得られる。
(electrode)
Examples of the metal material of the electrodes of the thermoelectric conversion element used in the present invention include copper, gold, nickel, aluminum, rhodium, platinum, chromium, palladium, stainless steel, molybdenum, and alloys containing any of these metals.
The thickness of the electrode layer is preferably 10 nm to 200 μm, more preferably 30 nm to 150 μm, and still more preferably 50 nm to 120 μm. When the thickness of the electrode layer is within the above range, the electric conductivity is high, the resistance is low, and sufficient strength as an electrode is obtained.
電極の形成は、前述した金属材料を用いて行う。
電極を形成する方法としては、樹脂フィルム上にパターンが形成されていない電極を設けた後、フォトリソグラフィー法を主体とした公知の物理的処理もしくは化学的処理、又はそれらを併用する等により、所定のパターン形状に加工する方法、または、スクリーン印刷法、インクジェット法等により直接電極のパターンを形成する方法等が挙げられる。
パターンが形成されていない電極の形成方法としては、真空蒸着法、スパッタリング法、イオンプレーティング法等のＰＶＤ（物理気相成長法）、もしくは熱ＣＶＤ、原子層蒸着（ＡＬＤ）等のＣＶＤ（化学気相成長法）等のドライプロセス、又はディップコーティング法、スピンコーティング法、スプレーコーティング法、グラビアコーティング法、ダイコーティング法、ドクターブレード法等の各種コーティングや電着法等のウェットプロセス、銀塩法、電解めっき法、無電解めっき法、金属箔の積層等が挙げられ、電極の材料に応じて適宜選択される。
本発明に用いる電極には、熱電性能を維持する観点から、高い導電性、高い熱伝導性が求められるため、めっき法や真空成膜法で成膜した電極を用いることが好ましい。高い導電性、高い熱伝導性を容易に実現できることから、真空蒸着法、スパッタリング法等の真空成膜法、および電解めっき法、無電解めっき法が好ましい。形成パターンの寸法、寸法精度の要求にもよるが、メタルマスク等のハードマスクを介し、容易にパターンを形成することもできる。
The electrodes are formed using the above-described metal material.
As a method of forming an electrode, after providing an electrode on which a pattern is not formed on a resin film, a predetermined physical or chemical treatment mainly using a photolithography method, or a combination thereof, or the like, is used. Or a method of directly forming an electrode pattern by a screen printing method, an ink jet method, or the like.
Examples of a method for forming an electrode on which no pattern is formed include PVD (physical vapor deposition) such as vacuum deposition, sputtering, and ion plating, or CVD (chemical vapor deposition) such as thermal CVD and atomic layer deposition (ALD). Dry processes such as vapor phase epitaxy), various coatings such as dip coating, spin coating, spray coating, gravure coating, die coating, and doctor blade, and wet processes such as electrodeposition, silver salt methods , An electrolytic plating method, an electroless plating method, lamination of a metal foil, and the like, which are appropriately selected according to the material of the electrode.
Since high conductivity and high thermal conductivity are required for the electrode used in the present invention from the viewpoint of maintaining thermoelectric performance, it is preferable to use an electrode formed by a plating method or a vacuum film forming method. Since high conductivity and high thermal conductivity can be easily realized, a vacuum film forming method such as a vacuum evaporation method and a sputtering method, an electrolytic plating method, and an electroless plating method are preferable. The pattern can be easily formed via a hard mask such as a metal mask, although it depends on the size and dimensional accuracy of the formed pattern.
＜熱電素子層＞
本発明の熱電変換素子を構成する熱電素子層（以下、「熱電素子層の薄膜」ということがある。）、すなわち、Ｐ型熱電素子層及びＮ型熱電素子層は、この順にＰ型熱電半導体材料、Ｎ型熱電半導体材料をそれぞれ含む熱電半導体組成物からなる。好ましくは、熱電半導体材料（以下、「熱電半導体微粒子」ということがある。）、耐熱性樹脂、並びにイオン液体及び／又は無機イオン性化合物を含む熱電半導体組成物からなる。
<Thermoelectric element layer>
The thermoelectric element layer constituting the thermoelectric conversion element of the present invention (hereinafter, sometimes referred to as a “thin film of the thermoelectric element layer”), that is, the P-type thermoelectric element layer and the N-type thermoelectric element layer are P-type thermoelectric semiconductors in this order. The thermoelectric semiconductor composition includes a material and an N-type thermoelectric semiconductor material. Preferably, it is composed of a thermoelectric semiconductor material (hereinafter, sometimes referred to as “thermoelectric semiconductor particles”), a heat-resistant resin, and an ionic liquid and / or an inorganic ionic compound.
（熱電半導体材料）
本発明に用いる熱電半導体材料、すなわち、Ｐ型熱電素子層、Ｎ型熱電素子層に含まれる熱電半導体材料としては、温度差を付与することにより、熱起電力を発生させることができる材料であれば特に制限されず、例えば、Ｐ型ビスマステルライド、Ｎ型ビスマステルライド等のビスマス−テルル系熱電半導体材料；ＧｅＴｅ、ＰｂＴｅ等のテルライド系熱電半導体材料；アンチモン−テルル系熱電半導体材料；ＺｎＳｂ、Ｚｎ３Ｓｂ２、Ｚｎ４Ｓｂ３等の亜鉛−アンチモン系熱電半導体材料；ＳｉＧｅ等のシリコン−ゲルマニウム系熱電半導体材料；Ｂｉ２Ｓｅ３等のビスマスセレナイド系熱電半導体材料；β―ＦｅＳｉ２、ＣｒＳｉ２、ＭｎＳｉ１．７３、Ｍｇ２Ｓｉ等のシリサイド系熱電半導体材料；酸化物系熱電半導体材料；ＦｅＶＡｌ、ＦｅＶＡｌＳｉ、ＦｅＶＴｉＡｌ等のホイスラー材料、ＴｉＳ２等の硫化物系熱電半導体材料等が用いられる。
これらの中で、ビスマス−テルル系熱電半導体材料、テルライド系熱電半導体材料、アンチモン−テルル系熱電半導体材料、又はビスマスセレナイド系熱電半導体材料が好ましい。
(Thermoelectric semiconductor material)
The thermoelectric semiconductor material used in the present invention, that is, the thermoelectric semiconductor material contained in the P-type thermoelectric element layer and the N-type thermoelectric element layer is a material that can generate a thermoelectromotive force by applying a temperature difference. if not particularly limited, e.g., P-type bismuth telluride, N-type bismuth telluride, etc. bismuth - telluride thermoelectric semiconductor material; GeTe, telluride based thermoelectric semiconductor materials such as PbTe; antimony - tellurium based thermoelectric semiconductor material; ZnSb, Zn 3 zinc Sb 2, Zn 4 Sb 3, etc. - antimony thermoelectric semiconductor material; SiGe like silicon - germanium thermoelectric semiconductor material; Bi 2 Se 3 bismuth selenide-based thermoelectric semiconductor materials such; β-FeSi 2, CrSi 2 , MnSi 1.73, silicide-based thermoelectric semiconductor materials, such as Mg 2 Si; oxide-based thermoelectric semiconductor Fee; FeVAl, FeVAlSi, Heusler materials such FeVTiAl, sulfide-based thermoelectric semiconductor materials such as TiS 2 is used.
Among these, a bismuth-tellurium-based thermoelectric semiconductor material, a telluride-based thermoelectric semiconductor material, an antimony-tellurium-based thermoelectric semiconductor material, or a bismuth selenide-based thermoelectric semiconductor material is preferable.
さらに、熱電性能の観点から、Ｐ型ビスマステルライド又はＮ型ビスマステルライド等のビスマス−テルル系熱電半導体材料であることがより好ましい。
前記Ｐ型ビスマステルライドは、キャリアが正孔で、ゼーベック係数が正値であり、例えば、ＢｉＸＴｅ３Ｓｂ２−Ｘで表わされるものが好ましく用いられる。この場合、Ｘは、好ましくは０＜Ｘ≦０．８であり、より好ましくは０．４≦Ｘ≦０．６である。Ｘが０より大きく０．８以下であるとゼーベック係数と電気伝導率が大きくなり、Ｐ型熱電素子としての特性が維持されるので好ましい。
また、前記Ｎ型ビスマステルライドは、キャリアが電子で、ゼーベック係数が負値であり、例えば、Ｂｉ２Ｔｅ３−ＹＳｅＹで表わされるものが好ましく用いられる。この場合、Ｙは、好ましくは０≦Ｙ≦３（Ｙ＝０の時：Ｂｉ２Ｔｅ３）であり、より好ましくは０＜Ｙ≦２．７である。Ｙが０以上３以下であるとゼーベック係数と電気伝導率が大きくなり、Ｎ型熱電素子としての特性が維持されるので好ましい。
Further, from the viewpoint of thermoelectric performance, a bismuth-tellurium-based thermoelectric semiconductor material such as P-type bismuth telluride or N-type bismuth telluride is more preferable.
As the P-type bismuth telluride, one having a carrier as a hole and a Seebeck coefficient as a positive value, for example, a compound represented by Bi X Te 3 Sb 2-X is preferably used. In this case, X is preferably 0 <X ≦ 0.8, and more preferably 0.4 ≦ X ≦ 0.6. When X is greater than 0 and 0.8 or less, the Seebeck coefficient and the electrical conductivity increase, which is preferable because characteristics as a P-type thermoelectric element are maintained.
Further, the N-type bismuth telluride, the carrier is an electron, the Seebeck coefficient is negative value, for example, those represented by Bi 2 Te 3-Y Se Y is preferably used. In this case, Y is preferably 0 ≦ Y ≦ 3 (when Y = 0: Bi 2 Te 3 ), and more preferably 0 <Y ≦ 2.7. When Y is 0 or more and 3 or less, the Seebeck coefficient and the electric conductivity increase, and the characteristics as an N-type thermoelectric element are preferably maintained.
熱電半導体組成物に用いる熱電半導体微粒子は、前述した熱電半導体材料を、微粉砕装置等により、所定のサイズまで粉砕したものである。 The thermoelectric semiconductor fine particles used in the thermoelectric semiconductor composition are obtained by pulverizing the above-described thermoelectric semiconductor material to a predetermined size using a pulverizer or the like.
熱電半導体微粒子の前記熱電半導体組成物中の配合量は、好ましくは、３０〜９９質量％である。より好ましくは、５０〜９６質量％であり、さらに好ましくは、７０〜９５質量％である。熱電半導体微粒子の配合量が、上記範囲内であれば、ゼーベック係数（ペルチェ係数の絶対値）が大きく、また電気伝導率の低下が抑制され、熱伝導率のみが低下するため高い熱電性能を示すとともに、十分な皮膜強度、屈曲性を有する膜が得られ好ましい。 The blending amount of the thermoelectric semiconductor fine particles in the thermoelectric semiconductor composition is preferably 30 to 99% by mass. More preferably, it is 50 to 96% by mass, and still more preferably 70 to 95% by mass. When the blending amount of the thermoelectric semiconductor fine particles is within the above range, the Seebeck coefficient (absolute value of the Peltier coefficient) is large, and the decrease in electric conductivity is suppressed, and only the heat conductivity is reduced, so that high thermoelectric performance is exhibited. In addition, a film having sufficient film strength and flexibility is obtained, which is preferable.
熱電半導体微粒子の平均粒径は、好ましくは、１０ｎｍ〜２００μｍ、より好ましくは、１０ｎｍ〜３０μｍ、さらに好ましくは、５０ｎｍ〜１０μｍ、特に好ましくは、１〜６μｍである。上記範囲内であれば、均一分散が容易になり、電気伝導率を高くすることができる。
前記熱電半導体材料を粉砕して熱電半導体微粒子を得る方法は特に限定されず、ジェットミル、ボールミル、ビーズミル、コロイドミル、ローラーミル等の公知の微粉砕装置等により、所定のサイズまで粉砕すればよい。
なお、熱電半導体微粒子の平均粒径は、レーザー回折式粒度分析装置（Ｍａｌｖｅｒｎ社製、マスターサイザー３０００）にて測定することにより得られ、粒径分布の中央値とした。
The average particle size of the thermoelectric semiconductor fine particles is preferably 10 nm to 200 μm, more preferably 10 nm to 30 μm, further preferably 50 nm to 10 μm, and particularly preferably 1 to 6 μm. Within the above range, uniform dispersion is facilitated, and electric conductivity can be increased.
The method of pulverizing the thermoelectric semiconductor material to obtain thermoelectric semiconductor fine particles is not particularly limited, and may be pulverized to a predetermined size by a known pulverizer such as a jet mill, a ball mill, a bead mill, a colloid mill, and a roller mill. .
The average particle size of the thermoelectric semiconductor fine particles was obtained by measuring with a laser diffraction particle size analyzer (manufactured by Malvern, Mastersizer 3000), and was defined as the median value of the particle size distribution.
また、熱電半導体微粒子は、事前に熱処理されたものであることが好ましい（ここでいう「熱処理」とは本発明でいうアニール処理工程で行う「アニール処理」とは異なる）。熱処理を行うことにより、熱電半導体微粒子は、結晶性が向上し、さらに、熱電半導体微粒子の表面酸化膜が除去されるため、熱電変換材料のゼーベック係数又はペルチェ係数が増大し、熱電性能指数をさらに向上させることができる。熱処理は、特に限定されないが、熱電半導体組成物を調製する前に、熱電半導体微粒子に悪影響を及ぼすことがないように、ガス流量が制御された、窒素、アルゴン等の不活性ガス雰囲気下、同じく水素等の還元ガス雰囲気下、または真空条件下で行うことが好ましく、不活性ガス及び還元ガスの混合ガス雰囲気下で行うことがより好ましい。具体的な温度条件は、用いる熱電半導体微粒子に依存するが、通常、微粒子の融点以下の温度で、かつ１００〜１５００℃で、数分〜数十時間行うことが好ましい。 Further, the thermoelectric semiconductor particles are preferably heat-treated in advance (the "heat treatment" here is different from the "annealing treatment" performed in the annealing treatment step in the present invention). By performing the heat treatment, the thermoelectric semiconductor particles have improved crystallinity, and further, since the surface oxide film of the thermoelectric semiconductor particles is removed, the Seebeck coefficient or the Peltier coefficient of the thermoelectric conversion material increases, and the thermoelectric performance index further increases. Can be improved. The heat treatment is not particularly limited, but before preparing the thermoelectric semiconductor composition, the gas flow rate is controlled so as not to adversely affect the thermoelectric semiconductor particles, under an atmosphere of an inert gas such as nitrogen or argon. The reaction is preferably performed under a reducing gas atmosphere such as hydrogen or under vacuum conditions, and more preferably under a mixed gas atmosphere of an inert gas and a reducing gas. The specific temperature condition depends on the thermoelectric semiconductor fine particles to be used, but it is usually preferable to perform the process at a temperature equal to or lower than the melting point of the fine particles and at 100 to 1500 ° C. for several minutes to several tens of hours.
（耐熱性樹脂）
本発明に用いる熱電半導体組成物には、熱電素子層を形成後、熱電半導体材料を高温度でアニール処理を行う観点から、耐熱性樹脂が好ましく用いられる。熱電半導体材料（熱電半導体微粒子）間のバインダーとして働き、熱電変換モジュールの屈曲性を高めることができるとともに、塗布等による薄膜の形成が容易になる。該耐熱性樹脂は、特に制限されるものではないが、熱電半導体組成物からなる薄膜をアニール処理等により熱電半導体微粒子を結晶成長させる際に、樹脂としての機械的強度及び熱伝導率等の諸物性が損なわれず維持される耐熱性樹脂が好ましい。
前記耐熱性樹脂は、耐熱性がより高く、且つ薄膜中の熱電半導体微粒子の結晶成長に悪影響を及ぼさないという点から、ポリアミド樹脂、ポリアミドイミド樹脂、ポリイミド樹脂、エポキシ樹脂が好ましく、屈曲性に優れるという点からポリアミド樹脂、ポリアミドイミド樹脂、ポリイミド樹脂がより好ましい。熱電変換素子の基板として、ポリイミドフィルムを用いた場合、該ポリイミドフィルムとの密着性などの点から、耐熱性樹脂としては、ポリイミド樹脂がより好ましい。なお、本発明においてポリイミド樹脂とは、ポリイミド及びその前駆体を総称する。
(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 after forming the thermoelectric element layer. It acts as a binder between the thermoelectric semiconductor materials (thermoelectric semiconductor particles), can increase the flexibility of the thermoelectric conversion module, and facilitates the formation of a thin film by coating or the like. The heat-resistant resin is not particularly limited. However, when a thin film of the thermoelectric semiconductor composition is subjected to crystal growth of thermoelectric semiconductor particles by annealing or the like, various properties such as mechanical strength and thermal conductivity of the resin are used. A heat-resistant resin that maintains its physical properties without deterioration is preferred.
The heat-resistant resin is preferably a polyamide resin, a polyamide-imide resin, a polyimide resin, or an epoxy resin, which has higher heat resistance and does not adversely affect the crystal growth of the thermoelectric semiconductor particles in the thin film, and has excellent flexibility. In this respect, a polyamide resin, a polyamideimide resin, and a polyimide resin are more preferable. When a polyimide film is used as the substrate of the thermoelectric conversion element, a polyimide resin is more preferable as the heat-resistant resin from the viewpoint of adhesion to the polyimide film. In the present invention, the polyimide resin is a general term for polyimide and its precursor.
前記耐熱性樹脂は、分解温度が３００℃以上であることが好ましい。分解温度が上記範囲であれば、後述するように、熱電半導体組成物からなる薄膜をアニール処理した場合でも、バインダーとして機能が失われることなく、屈曲性を維持することができる。 The heat-resistant resin preferably has a decomposition temperature of 300 ° C. or higher. When the decomposition temperature is in the above range, as described later, even when the thin film made of the thermoelectric semiconductor composition is annealed, the flexibility can be maintained without losing the function as a binder.
また、前記耐熱性樹脂は、熱重量測定（ＴＧ）による３００℃における質量減少率が１０％以下であることが好ましく、５％以下であることがより好ましく、１％以下であることがさらに好ましい。質量減少率が上記範囲であれば、後述するように、熱電半導体組成物からなる薄膜をアニール処理した場合でも、バインダーとして機能が失われることなく、熱電素子層の屈曲性を維持することができる。 Further, the heat-resistant resin preferably has a mass reduction rate at 300 ° C. by thermogravimetry (TG) of 10% or less, more preferably 5% or less, and still more preferably 1% or less. . If the mass reduction rate is within the above range, as described later, even when the thin film made of the thermoelectric semiconductor composition is annealed, the flexibility of the thermoelectric element layer can be maintained without losing the function as a binder. .
前記耐熱性樹脂の前記熱電半導体組成物中の配合量は、０．１〜４０質量％、好ましくは０．５〜２０質量％、より好ましくは、１〜２０質量％、さらに好ましくは２〜１５質量％である。前記耐熱性樹脂の配合量が、上記範囲内であると、熱電半導体材料のバインダーとし機能し、薄膜の形成がしやすくなり、しかも高い熱電性能と皮膜強度が両立した膜が得られる。 The compounding amount of the heat-resistant resin in the thermoelectric semiconductor composition is 0.1 to 40% by mass, preferably 0.5 to 20% by mass, more preferably 1 to 20% by mass, and further preferably 2 to 15% by mass. % By mass. When the compounding amount of the heat-resistant resin is within the above range, it functions as a binder of the thermoelectric semiconductor material, facilitates formation of a thin film, and obtains a film having both high thermoelectric performance and high film strength.
（イオン液体）
本発明で用いるイオン液体は、カチオンとアニオンとを組み合わせてなる溶融塩であり、−５０〜５００℃の温度領域のいずれかの温度領域において、液体で存在し得る塩をいう。イオン液体は、蒸気圧が極めて低く不揮発性であること、優れた熱安定性及び電気化学安定性を有していること、粘度が低いこと、かつイオン伝導度が高いこと等の特徴を有しているため、導電補助剤として、熱電半導体微粒子間の電気伝導率の低減を効果的に抑制することができる。また、イオン液体は、非プロトン性のイオン構造に基づく高い極性を示し、耐熱性樹脂との相溶性に優れるため、熱電素子層の電気伝導率を均一にすることができる。
(Ionic liquid)
The ionic liquid used in the present invention is a molten salt obtained by combining a cation and an anion, and refers to a salt that can exist as a liquid in any temperature range of -50 to 500 ° C. Ionic liquids have features such as extremely low vapor pressure, non-volatility, excellent thermal stability and electrochemical stability, low viscosity, and high ionic conductivity. Therefore, as a conductive auxiliary agent, it is possible to effectively suppress a decrease in electric conductivity between the thermoelectric semiconductor particles. Further, the ionic liquid has a high polarity based on the aprotic ionic structure and has excellent compatibility with the heat-resistant resin, so that the electric conductivity of the thermoelectric element layer can be made uniform.
イオン液体は、公知または市販のものが使用できる。例えば、ピリジニウム、ピリミジニウム、ピラゾリウム、ピロリジニウム、ピペリジニウム、イミダゾリウム等の窒素含有環状カチオン化合物及びそれらの誘導体；テトラアルキルアンモニウムのアミン系カチオン及びそれらの誘導体；ホスホニウム、トリアルキルスルホニウム、テトラアルキルホスホニウム等のホスフィン系カチオン及びそれらの誘導体；リチウムカチオン及びその誘導体等のカチオン成分と、Ｃｌ−、ＡｌＣｌ４ −、Ａｌ２Ｃｌ７ −、ＣｌＯ４ −等の塩化物イオン、Ｂｒ−等の臭化物イオン、Ｉ−等のヨウ化物イオン、ＢＦ４ −、ＰＦ６ −等のフッ化物イオン、Ｆ（ＨＦ）ｎ −等のハロゲン化物アニオン、ＮＯ３ −、ＣＨ３ＣＯＯ−、ＣＦ３ＣＯＯ−、ＣＨ３ＳＯ３ −、ＣＦ３ＳＯ３ −、（ＦＳＯ２）２Ｎ−、（ＣＦ３ＳＯ２）２Ｎ−、（ＣＦ３ＳＯ２）３Ｃ−、ＡｓＦ６ −、ＳｂＦ６ −、ＮｂＦ６ −、ＴａＦ６ −、Ｆ（ＨＦ）ｎ−、（ＣＮ）２Ｎ−、Ｃ４Ｆ９ＳＯ３ −、（Ｃ２Ｆ５ＳＯ２）２Ｎ−、Ｃ３Ｆ７ＣＯＯ−、（ＣＦ３ＳＯ２）（ＣＦ３ＣＯ）Ｎ−等のアニオン成分とから構成されるものが挙げられる。 Known or commercially available ionic liquids can be used. For example, nitrogen-containing cyclic cation compounds such as pyridinium, pyrimidinium, pyrazolium, pyrrolidinium, piperidinium, imidazolium and derivatives thereof; amine cations of tetraalkylammonium and derivatives thereof; phosphines such as phosphonium, trialkylsulfonium and tetraalkylphosphonium systems cations and their derivatives; and cationic components, such as lithium cations and derivatives thereof, Cl -, AlCl 4 -, Al 2 Cl 7 -, ClO 4 - chloride or ion, Br -, etc. of bromide ion, I -, etc. , Fluoride ions such as BF 4 − and PF 6 − , halide anions such as F (HF) n − , 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 anion And a component.
上記のイオン液体の中で、高温安定性、熱電半導体微粒子及び樹脂との相溶性、熱電半導体微粒子間隙の電気伝導率の低下抑制等の観点から、イオン液体のカチオン成分が、ピリジニウムカチオン及びその誘導体、イミダゾリウムカチオン及びその誘導体から選ばれる少なくとも１種を含むことが好ましい。イオン液体のアニオン成分が、ハロゲン化物アニオンを含むことが好ましく、Ｃｌ−、Ｂｒ−及びＩ−から選ばれる少なくとも１種を含むことがさらに好ましい。 Among the above ionic liquids, the cation component of the ionic liquid is a pyridinium cation and a derivative thereof from the viewpoints of high-temperature stability, compatibility with the thermoelectric semiconductor fine particles and the resin, and suppression of a decrease in electric conductivity in the gap between the thermoelectric semiconductor fine particles. , And at least one selected from imidazolium cations and derivatives thereof. The anion component of the ionic liquid preferably contains a halide anion, and more preferably contains at least one selected from Cl − , Br − and I − .
カチオン成分が、ピリジニウムカチオン及びその誘導体を含むイオン液体の具体的な例として、４−メチル−ブチルピリジニウムクロライド、３−メチル−ブチルピリジニウムクロライド、４−メチル−ヘキシルピリジニウムクロライド、３−メチル−ヘキシルピリジニウムクロライド、４−メチル−オクチルピリジニウムクロライド、３−メチル−オクチルピリジニウムクロライド、３、４−ジメチル−ブチルピリジニウムクロライド、３、５−ジメチル−ブチルピリジニウムクロライド、４−メチル−ブチルピリジニウムテトラフルオロボレート、４−メチル−ブチルピリジニウムヘキサフルオロホスフェート、１-ブチル-４-メチルピリジニウムブロミド、１-ブチル-４-メチルピリジニウムヘキサフルオロホスファート、１-ブチル-４-メチルピリジニウムヨージド等が挙げられる。この中で、１−ブチル−４−メチルピリジニウムブロミド、１−ブチル−４−メチルピリジニウムヘキサフルオロホスファート、１-ブチル-４-メチルピリジニウムヨージドが好ましい。 Specific examples of the ionic liquid in which the cation component contains a pyridinium cation and a derivative thereof include 4-methyl-butylpyridinium chloride, 3-methyl-butylpyridinium chloride, 4-methyl-hexylpyridinium chloride, and 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-butyl-4-methylpyridinium bromide, 1-butyl-4-methylpyridinium hexafluorophosphate, 1-butyl-4-methyl Lupi lysine iodide and the like. Among them, 1-butyl-4-methylpyridinium bromide, 1-butyl-4-methylpyridinium hexafluorophosphate, and 1-butyl-4-methylpyridinium iodide are preferred.
また、カチオン成分が、イミダゾリウムカチオン及びその誘導体を含むイオン液体の具体的な例として、［１−ブチル−３−（２−ヒドロキシエチル）イミダゾリウムブロミド］、［１−ブチル−３−（２−ヒドロキシエチル）イミダゾリウムテトラフルオロボレイト］、１−エチル−３−メチルイミダゾリウムクロライド、１−エチル−３−メチルイミダゾリウムブロミド、１−ブチル−３−メチルイミダゾリウムクロライド、１−ヘキシル−３−メチルイミダゾリウムクロライド、１−オクチル−３−メチルイミダゾリウムクロライド、１−デシル−３−メチルイミダゾリウムクロライド、１−デシル−３−メチルイミダゾリウムブロミド、１−ドデシル−３−メチルイミダゾリウムクロライド、１−テトラデシル−３−メチルイミダゾリウムクロライド、１−エチル−３−メチルイミダゾリウムテトラフロオロボレート、１−ブチル−３−メチルイミダゾリウムテトラフロオロボレート、１−ヘキシル−３−メチルイミダゾリウムテトラフロオロボレート、１−エチル−３−メチルイミダゾリウムヘキサフルオロホスフェート、１−ブチル−３−メチルイミダゾリウムヘキサフルオロホスフェート、１−メチル−３−ブチルイミダゾリウムメチルスルフェート、１、３−ジブチルイミダゾリウムメチルスルフェート等が挙げられる。この中で、［１−ブチル−３−（２−ヒドロキシエチル）イミダゾリウムブロミド］、［１−ブチル−３−（２−ヒドロキシエチル）イミダゾリウムテトラフルオロボレイト］が好ましい。 Specific examples of the ionic liquid in which the cation component contains an imidazolium cation and a derivative thereof include [1-butyl-3- (2-hydroxyethyl) imidazolium bromide] and [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-methylimidazo Um chloride, 1-ethyl-3-methylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium tetrafluoroborate, 1-hexyl-3-methylimidazolium tetrafluoroborate, 1-ethyl-3 -Methylimidazolium hexafluorophosphate, 1-butyl-3-methylimidazolium hexafluorophosphate, 1-methyl-3-butylimidazolium methylsulfate, 1,3-dibutylimidazolium methylsulfate and the like. Among them, [1-butyl-3- (2-hydroxyethyl) imidazolium bromide] and [1-butyl-3- (2-hydroxyethyl) imidazolium tetrafluoroborate] are preferable.
上記のイオン液体は、電気伝導率が１０−７Ｓ／ｃｍ以上であることが好ましく、１０−６Ｓ／ｃｍ以上であることがより好ましい。電気伝導率が上記の範囲であれば、導電補助剤として、熱電半導体微粒子間の電気伝導率の低減を効果的に抑制することができる。 The above ionic liquid preferably has an electric conductivity of 10 −7 S / cm or more, and more preferably 10 −6 S / cm or more. When the electric conductivity is in the above range, a decrease in electric conductivity between the thermoelectric semiconductor particles can be effectively suppressed as a conductive auxiliary agent.
また、上記のイオン液体は、分解温度が３００℃以上であることが好ましい。分解温度が上記範囲であれば、後述するように、熱電半導体組成物からなる薄膜をアニール処理した場合でも、導電補助剤としての効果を維持することができる。 Further, the ionic liquid preferably has a decomposition temperature of 300 ° C. or higher. When the decomposition temperature is in the above range, the effect as a conductive auxiliary agent can be maintained even when a thin film made of a thermoelectric semiconductor composition is annealed, as described later.
また、上記のイオン液体は、熱重量測定（ＴＧ）による３００℃における質量減少率が１０％以下であることが好ましく、５％以下であることがより好ましく、１％以下であることがさらに好ましい。質量減少率が上記範囲であれば、後述するように、熱電半導体組成物からなる薄膜をアニール処理した場合でも、導電補助剤としての効果を維持することができる。 Further, the ionic liquid has a mass reduction rate at 300 ° C. by thermogravimetry (TG) of preferably 10% or less, more preferably 5% or less, and still more preferably 1% or less. . When the mass reduction rate is in the above range, as described later, even when the thin film made of the thermoelectric semiconductor composition is annealed, the effect as the conductive auxiliary agent can be maintained.
前記イオン液体の前記熱電半導体組成物中の配合量は、好ましくは０．０１〜５０質量％、より好ましくは０．５〜３０質量％、さらに好ましくは１．０〜２０質量％である。前記イオン液体の配合量が、上記の範囲内であれば、電気伝導率の低下が効果的に抑制され、高い熱電性能を有する膜が得られる。 The compounding amount of the ionic liquid in the thermoelectric semiconductor composition is preferably 0.01 to 50% by mass, more preferably 0.5 to 30% by mass, and further preferably 1.0 to 20% by mass. When the blending amount of the ionic liquid is within the above range, a decrease in electric conductivity is effectively suppressed, and a film having high thermoelectric performance is obtained.
（無機イオン性化合物）
本発明で用いる無機イオン性化合物は、少なくともカチオンとアニオンから構成される化合物である。無機イオン性化合物は室温において固体であり、４００〜９００℃の温度領域のいずれかの温度に融点を有し、イオン伝導度が高いこと等の特徴を有しているため、導電補助剤として、熱電半導体微粒子間の電気伝導率の低減を抑制することができる。
(Inorganic ionic compound)
The inorganic ionic compound used in the present invention is a compound composed of at least a cation and an anion. The inorganic ionic compound is solid at room temperature, has a melting point at any temperature in the temperature range of 400 to 900 ° C., and has characteristics such as high ionic conductivity. It is possible to suppress a decrease in the electrical conductivity between the thermoelectric semiconductor particles.
カチオンとしては、金属カチオンを用いる。
金属カチオンとしては、例えば、アルカリ金属カチオン、アルカリ土類金属カチオン、典型金属カチオン及び遷移金属カチオンが挙げられ、アルカリ金属カチオン又はアルカリ土類金属カチオンがより好ましい。
アルカリ金属カチオンとしては、例えば、Ｌｉ＋、Ｎａ＋、Ｋ＋、Ｒｂ＋、Ｃｓ＋及びＦｒ＋等が挙げられる。
アルカリ土類金属カチオンとしては、例えば、Ｍｇ２＋、Ｃａ２＋、Ｓｒ２＋及びＢａ２＋等が挙げられる。
As the cation, a metal cation is used.
Examples of the metal cation include an alkali metal cation, an alkaline earth metal cation, a typical metal cation, and a transition metal cation, and an alkali metal cation or an alkaline earth metal cation is more preferable.
Examples of the alkali metal cation include Li + , Na + , K + , Rb + , Cs +, and Fr + .
Examples of the alkaline earth metal cation include Mg 2+ , Ca 2+ , Sr 2+ and Ba 2+ .
アニオンとしては、例えば、Ｆ−、Ｃｌ−、Ｂｒ−、Ｉ−、ＯＨ−、ＣＮ−、ＮＯ３−、ＮＯ２−、ＣｌＯ−、ＣｌＯ２−、ＣｌＯ３−、ＣｌＯ４−、ＣｒＯ４ ２−、ＨＳＯ４ −、ＳＣＮ−、ＢＦ４ −、ＰＦ６ −等が挙げられる。 The anion such as, 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.
無機イオン性化合物は、公知または市販のものが使用できる。例えば、カリウムカチオン、ナトリウムカチオン、又はリチウムカチオン等のカチオン成分と、Ｃｌ−、ＡｌＣｌ４ −、Ａｌ２Ｃｌ７ −、ＣｌＯ４ −等の塩化物イオン、Ｂｒ−等の臭化物イオン、Ｉ−等のヨウ化物イオン、ＢＦ４ −、ＰＦ６ −等のフッ化物イオン、Ｆ（ＨＦ）ｎ −等のハロゲン化物アニオン、ＮＯ３ −、ＯＨ−、ＣＮ−等のアニオン成分とから構成されるものが挙げられる。 Known or commercially available inorganic ionic compounds can be used. For example, a cation component such as a potassium cation, a sodium cation, or a lithium cation, a chloride ion such as Cl − , AlCl 4 − , Al 2 Cl 7 − , and ClO 4 − , a bromide ion such as Br − , and an I − etc. Examples thereof include those composed of iodide ions, fluoride ions such as BF 4 − and PF 6 − , halide anions such as F (HF) n − and anion components such as NO 3 − , OH − and CN −. Can be
上記の無機イオン性化合物の中で、高温安定性、熱電半導体微粒子及び樹脂との相溶性、熱電半導体微粒子間隙の電気伝導率の低下抑制等の観点から、無機イオン性化合物のカチオン成分が、カリウム、ナトリウム、及びリチウムから選ばれる少なくとも１種を含むことが好ましい。また、無機イオン性化合物のアニオン成分が、ハロゲン化物アニオンを含むことが好ましく、Ｃｌ−、Ｂｒ−、及びＩ−から選ばれる少なくとも１種を含むことがさらに好ましい。 Among the above-mentioned inorganic ionic compounds, from the viewpoints of high-temperature stability, compatibility with the thermoelectric semiconductor fine particles and the resin, suppression of a decrease in electric conductivity between the thermoelectric semiconductor fine particles, the cation component of the inorganic ionic compound is potassium. , Sodium, and lithium. The anionic component of the inorganic ionic compound preferably contains a halide anion, and more preferably contains at least one selected from Cl − , Br − , and I − .
カチオン成分が、カリウムカチオンを含む無機イオン性化合物の具体的な例として、ＫＢｒ、ＫＩ、ＫＣｌ、ＫＦ、ＫＯＨ、Ｋ２ＣＯ３等が挙げられる。この中で、ＫＢｒ、ＫＩが好ましい。
カチオン成分が、ナトリウムカチオンを含む無機イオン性化合物の具体的な例として、ＮａＢｒ、ＮａＩ、ＮａＯＨ、ＮａＦ、Ｎａ２ＣＯ３等が挙げられる。この中で、ＮａＢｒ、ＮａＩが好ましい。
カチオン成分が、リチウムカチオンを含む無機イオン性化合物の具体的な例として、ＬｉＦ、ＬｉＯＨ、ＬｉＮＯ３等が挙げられる。この中で、ＬｉＦ、ＬｉＯＨが好ましい。
Specific examples of the inorganic ionic compound in which the cation component contains a potassium cation include KBr, KI, KCl, KF, KOH, and K 2 CO 3 . Among them, KBr and KI are preferable.
Specific examples of the inorganic ionic compound in which the cation component contains a sodium cation include NaBr, NaI, NaOH, NaF, and Na 2 CO 3 . Of these, NaBr and NaI are preferred.
Specific examples of the inorganic ionic compound whose cation component includes a lithium cation include LiF, LiOH, and LiNO 3 . Among them, LiF and LiOH are preferable.
上記の無機イオン性化合物は、電気伝導率が１０−７Ｓ／ｃｍ以上であることが好ましく、１０−６Ｓ／ｃｍ以上であることがより好ましい。電気伝導率が上記範囲であれば、導電補助剤として、熱電半導体微粒子間の電気伝導率の低減を効果的に抑制することができる。 The above-mentioned inorganic ionic compound preferably has an electric conductivity of 10 −7 S / cm or more, more preferably 10 −6 S / cm or more. When the electric conductivity is in the above range, reduction in electric conductivity between the thermoelectric semiconductor particles can be effectively suppressed as a conductive auxiliary agent.
また、上記の無機イオン性化合物は、分解温度が４００℃以上であることが好ましい。分解温度が上記範囲であれば、後述するように、熱電半導体組成物からなる薄膜をアニール処理した場合でも、導電補助剤としての効果を維持することができる。 Further, the above-mentioned inorganic ionic compound preferably has a decomposition temperature of 400 ° C. or higher. When the decomposition temperature is in the above range, the effect as a conductive auxiliary agent can be maintained even when a thin film made of a thermoelectric semiconductor composition is annealed, as described later.
また、上記の無機イオン性化合物は、熱重量測定（ＴＧ）による４００℃における質量減少率が１０％以下であることが好ましく、５％以下であることがより好ましく、１％以下であることがさらに好ましい。質量減少率が上記範囲であれば、後述するように、熱電半導体組成物からなる熱電素子層の薄膜をアニール処理した場合でも、導電補助剤としての効果を維持することができる。 In addition, the inorganic ionic compound preferably has a mass reduction rate at 400 ° C. by thermogravimetry (TG) of 10% or less, more preferably 5% or less, and more preferably 1% or less. More preferred. When the mass reduction rate is in the above range, as described later, even when the thin film of the thermoelectric element layer made of the thermoelectric semiconductor composition is annealed, the effect as the conductive auxiliary agent can be maintained.
前記無機イオン性化合物の前記熱電半導体組成物中の配合量は、好ましくは０．０１〜５０質量％、より好ましくは０．５〜３０質量％、さらに好ましくは１．０〜１０質量％である。前記無機イオン性化合物の配合量が、上記範囲内であれば、電気伝導率の低下を効果的に抑制でき、結果として熱電性能が向上した膜が得られる。
なお、無機イオン性化合物とイオン液体とを併用する場合においては、前記熱電半導体組成物中における、無機イオン性化合物及びイオン液体の含有量の総量は、好ましくは０．０１〜５０質量％、より好ましくは０．５〜３０質量％、さらに好ましくは１．０〜１０質量％である。
The compounding amount of the inorganic ionic compound in the thermoelectric semiconductor composition is preferably 0.01 to 50% by mass, more preferably 0.5 to 30% by mass, and further preferably 1.0 to 10% by mass. . When the amount of the inorganic ionic compound is within the above range, a decrease in electric conductivity can be effectively suppressed, and as a result, a film having improved thermoelectric performance can be obtained.
When the inorganic ionic compound and the 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 to 50% by mass, Preferably it is 0.5 to 30% by mass, more preferably 1.0 to 10% by mass.
（その他の添加剤）
本発明で用いる熱電半導体組成物には、上記以外の成分以外に、必要に応じて、さらに分散剤、造膜助剤、光安定剤、酸化防止剤、粘着付与剤、可塑剤、着色剤、樹脂安定剤、充てん剤、顔料、導電性フィラー、導電性高分子、硬化剤等の他の添加剤を含んでいてもよい。これらの添加剤は、１種単独で、あるいは２種以上を組み合わせて用いることができる。
(Other additives)
The thermoelectric semiconductor composition used in the present invention, in addition to the components other than the above, if necessary, further dispersant, film forming aid, light stabilizer, antioxidant, tackifier, plasticizer, colorant, Other additives such as a resin stabilizer, a filler, a pigment, a conductive filler, a conductive polymer, and a curing agent may be included. These additives can be used alone or in combination of two or more.
（熱電半導体組成物の調製方法）
本発明で用いる熱電半導体組成物の調製方法は、特に制限はなく、超音波ホモジナイザー、スパイラルミキサー、プラネタリーミキサー、ディスパーサー、ハイブリッドミキサー等の公知の方法により、前記熱電半導体微粒子、前記耐熱性樹脂、並びに前記イオン液体及び／又は無機イオン性化合物、必要に応じて前記その他の添加剤、さらに溶媒を加えて、混合分散させ、当該熱電半導体組成物を調製すればよい。
前記溶媒としては、例えば、トルエン、酢酸エチル、メチルエチルケトン、アルコール、テトラヒドロフラン、メチルピロリドン、エチルセロソルブ等の溶媒などが挙げられる。これらの溶媒は、１種を単独で用いてもよく、２種以上を混合して用いてもよい。熱電半導体組成物の固形分濃度としては、該組成物が塗工に適した粘度であればよく、特に制限はない。
(Method of preparing thermoelectric semiconductor composition)
The method for preparing the thermoelectric semiconductor composition used in the present invention is not particularly limited, and the thermoelectric semiconductor particles and the heat-resistant resin can be obtained by a known method such as an ultrasonic homogenizer, a spiral mixer, a planetary mixer, a disperser, and a hybrid mixer. The thermoelectric semiconductor composition may be prepared by adding the ionic liquid and / or the inorganic ionic compound, the other additives as needed, and the solvent, and mixing and dispersing the mixture.
Examples of the solvent include solvents such as toluene, ethyl acetate, methyl ethyl ketone, alcohol, tetrahydrofuran, methylpyrrolidone, and ethyl cellosolve. These solvents may be used alone or as a mixture of two or more. The solid content concentration of the thermoelectric semiconductor composition is not particularly limited as long as the composition has a viscosity suitable for coating.
前記熱電半導体組成物からなる熱電素子層の薄膜は、本発明に用いたパターン層の開口部に、前記熱電半導体組成物を充填、及び乾燥することで形成することができる。このように、熱電素子層を形成することで、パターン層の開口部の形状が反映された形状制御性が優れた熱電素子層が得られる。 The thin film of the thermoelectric element layer composed of the thermoelectric semiconductor composition can be formed by filling the opening of the pattern layer used in the present invention with the thermoelectric semiconductor composition and drying. By forming the thermoelectric element layer in this manner, a thermoelectric element layer having excellent shape controllability reflecting the shape of the opening of the pattern layer can be obtained.
＜アニール処理＞
前記熱電半導体組成物を充填、及び乾燥することにより形成した熱電素子層、すなわち、Ｐ型熱電素子層及びＮ型熱電素子層は、さらに、アニール処理を行うことで、熱電性能を安定化させるとともに、熱電素子層中の熱電半導体微粒子を結晶成長させることができ、熱電性能をさらに向上させることができる。
<Annealing treatment>
The thermoelectric element layer formed by filling and drying the thermoelectric semiconductor composition, that is, the P-type thermoelectric element layer and the N-type thermoelectric element layer further stabilize thermoelectric performance by performing an annealing treatment. In addition, the thermoelectric semiconductor particles in the thermoelectric element layer can be crystal-grown, and the thermoelectric performance can be further improved.
アニール処理は、特に限定されないが、通常、ガス流量が制御された、窒素、アルゴン等の不活性ガス雰囲気下、還元ガス雰囲気下、または真空条件下で行われ、用いる耐熱性樹脂、イオン液体、無機イオン性化合物、また、基板、パターン層として用いた樹脂を含む層等の耐熱温度等に依存するが、アニール処理の温度は、通常１００〜６００℃で、数分〜数十時間、好ましくは１５０〜５５０℃で、数分〜数十時間、より好ましくは２００〜５００℃で、数分〜数十時間行う。 The annealing treatment is not particularly limited, but is usually performed under a controlled gas flow rate, under an inert gas atmosphere such as nitrogen or argon, under a reducing gas atmosphere, or under vacuum conditions. Although depending on the heat resistance temperature of the inorganic ionic compound, the substrate, the layer containing the resin used as the pattern layer, etc., the temperature of the annealing treatment is usually 100 to 600 ° C., for several minutes to several tens of hours, preferably The reaction is performed at 150 to 550 ° C. for several minutes to several tens hours, more preferably at 200 to 500 ° C. for several minutes to several tens hours.
前記熱電半導体組成物からなる熱電素子層の薄膜の厚さは、特に制限はないが、熱電性能と皮膜強度の点から、好ましくは１００ｎｍ〜１０００μｍ、より好ましくは１〜６００μｍ、さらに好ましくは１０〜４００μｍ、特に好ましくは、１０〜３００μｍである。 The thickness of the thin film of the thermoelectric element layer composed of the thermoelectric semiconductor composition is not particularly limited, but is preferably 100 nm to 1000 μm, more preferably 1 to 600 μm, and still more preferably 10 to 100 μm from the viewpoint of thermoelectric performance and film strength. It is 400 μm, particularly preferably 10 to 300 μm.
本発明の熱電変換素子は、熱電素子層の形状制御性が優れ、電極部との接合性が向上する観点から、前述したπ型の熱電変換素子に適用することが好ましい。π型の熱電変換素子の構成は、例えば、互いに離間するー対の電極を基板上に設け、―方の電極の上にＰ型熱電素子層を、他方の電極の上にＮ型熱電素子層を、同じく互いに離間して設け、両方の熱電素子層の上面を対向する基板上の電極に電気的に直列接続することで構成される。高い熱電性能を効率良く得る観点から、対向する基板の電極を介したＰ型熱電素子層及びＮ型熱電素子層を複数組、電気的に直列接続して用いることが好ましい。 The thermoelectric conversion element of the present invention is preferably applied to the above-mentioned π-type thermoelectric conversion element, from the viewpoint of excellent controllability of the shape of the thermoelectric element layer and improvement of the bondability with the electrode portion. The configuration of a π-type thermoelectric conversion element is, for example, to provide a pair of electrodes separated from each other on a substrate, a P-type thermoelectric element layer on the negative electrode, and an N-type thermoelectric element layer on the other electrode. Are also separated from each other, and the upper surfaces of both thermoelectric element layers are electrically connected in series to the electrodes on the opposing substrate. From the viewpoint of efficiently obtaining high thermoelectric performance, it is preferable to use a plurality of sets of the P-type thermoelectric element layers and the N-type thermoelectric element layers via electrodes of the opposing substrate, which are electrically connected in series.
［熱電変換素子の製造方法］
本発明の熱電変換素子の製造方法は、電極を有する基板と、離間した開口部を複数有するパターン層と、前記離間した開口部内にＰ型熱電素子層及びＮ型熱電素子層と、を含む熱電変換素子において、前記パターン層が樹脂を含む層であり、前記Ｐ型熱電素子層及びＮ型熱電素子層が熱電半導体材料を含む熱電半導体組成物からなる、熱電変換素子の製造方法であって、前記電極上に離間した開口部を有するパターン層を形成する工程、前記離間した開口部にＰ型熱電半導体材料を含む熱電半導体組成物及びＮ型熱電半導体材料を含む熱電半導体組成物をそれぞれ充填する工程、前記離間した開口部に充填された、前記Ｐ型熱電半導体材料を含む熱電半導体組成物及び前記Ｎ型熱電半導体材料を含む熱電半導体組成物を乾燥し、Ｐ型熱電素子層及びＮ型熱電素子層を得る工程、並びに得られたＰ型熱電素子層及びＮ型熱電素子層をアニール処理する工程を含むことを特徴とする。
以下、本発明の熱電変換素子の製造方法について、図を用いて説明する。
[Method of manufacturing thermoelectric conversion element]
A method for manufacturing a thermoelectric conversion element according to the present invention includes a thermoelectric element including a substrate having electrodes, a pattern layer having a plurality of spaced openings, and a P-type thermoelectric element layer and an N-type thermoelectric element layer in the spaced openings. In the conversion element, the pattern layer is a layer containing a resin, the P-type thermoelectric element layer and the N-type thermoelectric element layer are made of a thermoelectric semiconductor composition containing a thermoelectric semiconductor material, a method for manufacturing a thermoelectric conversion element, Forming a pattern layer having a separated opening on the electrode, filling the separated opening with a thermoelectric semiconductor composition containing a P-type thermoelectric semiconductor material and a thermoelectric semiconductor composition containing an N-type thermoelectric semiconductor material, respectively; Drying the thermoelectric semiconductor composition containing the P-type thermoelectric semiconductor material and the N-type thermoelectric semiconductor material filled in the spaced openings; And obtaining the N-type thermoelectric element layer process, characterized in that it comprises a step of the P-type thermoelectric element layer and N-type thermoelectric element layer obtained as well annealed.
Hereinafter, a method for manufacturing a thermoelectric conversion element of the present invention will be described with reference to the drawings.
図３は、本発明の熱電変換素子の製造方法に従った工程の一例を工程順に示す説明図
であり、（ａ）は基板上に電極を形成した後の断面図であり、（ｂ）は電極上に樹脂を含む層を形成した後の断面図であり、（ｃ）は樹脂を含む層に開口部を形成した後のパターン層の平面図（電極部は図示せず）であり、（ｃ’）は（ｃ）においてＡ−Ａ’間で切断した時のパターン層の断面図であり、（ｄ）はパターン層の開口部に熱電素子層を充填した後の断面図であり、（ｅ）は（ｄ）で得られた熱電素子層の上面と、これに対向する基板上の電極とを対向させ接合する態様を示す断面図である。これにより、熱電変換素子を得ることができる。
FIG. 3 is an explanatory view showing an example of steps in accordance with the method for manufacturing a thermoelectric conversion element of the present invention in the order of steps, (a) is a cross-sectional view after forming electrodes on a substrate, and (b) is It is sectional drawing after forming the layer containing resin on an electrode, (c) is a top view of the pattern layer after opening is formed in the layer containing resin (electrode part is not shown), (c ′) is a cross-sectional view of the pattern layer when cut along AA ′ in (c), (d) is a cross-sectional view after filling the thermoelectric element layer into the opening of the pattern layer, (e) is a cross-sectional view showing a mode in which the upper surface of the thermoelectric element layer obtained in (d) and an electrode on the substrate facing the thermoelectric element layer are opposed to each other and joined. Thereby, a thermoelectric conversion element can be obtained.
＜パターン層形成工程＞
パターン層形成工程は、基板の電極上に樹脂を含む層からなるパターン層を形成する工程である。例えば、図３（ｂ）においては、（ａ）で準備した基板１２ａの電極１３ａ上に、樹脂を含む層１４’を塗布し、（ｃ）及び（ｃ’）の離間した開口１５ｓ、開口部１５を有するパターン層１４を形成する工程である。
<Pattern layer forming step>
The pattern layer forming step is a step of forming a pattern layer made of a layer containing a resin on the electrode of the substrate. For example, in FIG. 3B, a layer 14 ′ containing a resin is applied on the electrode 13 a of the substrate 12 a prepared in FIG. 3A, and the openings 15 s and the openings 15 c shown in FIGS. This is a step of forming the pattern layer 14 having the pattern 15.
パターン層を形成する方法としては、特に制限されないが、パターン精度の観点から、前述したように、樹脂を含む層として、感光性樹脂組成物を用いる場合は、フォトリソグラフィー法を主体とした公知の方法を用いることができ、フォトマスク等を用い簡便にパターン層を得ることができる。また、樹脂を含む層として、感光性を有さない樹脂組成物を用いる場合も同様に、前述したように、フォトリソグラフィー法を主体とした公知の方法を用いることができる。さらに、前述したように、レーザー加工法で樹脂を含む層を直接パターン加工する方法を用いることができる。 The method of forming the pattern layer is not particularly limited, but from the viewpoint of pattern accuracy, as described above, when a photosensitive resin composition is used as the layer containing a resin, a known photolithography method is mainly used. A pattern layer can be easily obtained using a photomask or the like. Similarly, when a resin composition having no photosensitivity is used as the resin-containing layer, a known method mainly using a photolithography method can be used as described above. Further, as described above, a method of directly patterning a layer containing a resin by a laser processing method can be used.
＜熱電素子層形成工程＞
熱電素子層形成工程は、熱電半導体組成物充填工程及び熱電半導体組成物乾燥工程を含む。
<Thermoelectric element layer forming step>
The thermoelectric element layer forming step includes a thermoelectric semiconductor composition filling step and a thermoelectric semiconductor composition drying step.
（熱電半導体組成物充填工程）
熱電半導体組成物充填工程は、パターン層形成工程で得られたパターン層の離間した開口部の内部にＰ型熱電半導体材料を含む熱電半導体組成物及びＮ型熱電半導体材料を含む熱電半導体組成物をそれぞれ充填する工程であり、例えば、図３（ｄ）においては、（ｃ）、（ｃ’）で準備した樹脂を含む層１４’からなるパターン層１４の開口１５ｓを有する開口部１５の内部に、Ｐ型熱電半導体材料を含む熱電半導体組成物及びＮ型熱電半導体材料を含む熱電半導体組成物をそれぞれ充填する工程である。
熱電半導体組成物を、パターン層の開口部の内部に充填する方法としては、スクリーン印刷法、フレキソ印刷法、グラビア印刷法、スピンコート法、ダイコート法、スプレーコート法、バーコート法、ドクターブレード法、ディスペンス法等の公知の方法が挙げられる。充填精度、製造効率の観点から、スクリーン印刷法、ステンシル印刷法、ディスペンス法を用いることが好ましい。
(Thermoelectric semiconductor composition filling step)
In the thermoelectric semiconductor composition filling step, the thermoelectric semiconductor composition including the P-type thermoelectric semiconductor material and the thermoelectric semiconductor composition including the N-type thermoelectric semiconductor material inside the spaced openings of the pattern layer obtained in the pattern layer forming step. Each of these is a filling step. For example, in FIG. 3D, the inside of the opening 15 having the opening 15s of the pattern layer 14 composed of the layer 14 ′ containing the resin prepared in (c) and (c ′) is formed. And filling a thermoelectric semiconductor composition containing a P-type thermoelectric semiconductor material and a thermoelectric semiconductor composition containing an N-type thermoelectric semiconductor material.
As a method of filling the inside of the opening of the pattern layer with the thermoelectric semiconductor composition, screen printing, flexographic printing, gravure printing, spin coating, die coating, spray coating, bar coating, doctor blade coating, etc. And a known method such as a dispensing method. From the viewpoint of filling accuracy and manufacturing efficiency, it is preferable to use a screen printing method, a stencil printing method, and a dispensing method.
（熱電半導体組成物乾燥工程）
熱電半導体組成物乾燥工程は、前記離間した開口部に充填された、前記Ｐ型熱電半導体材料を含む熱電半導体組成物及び前記Ｎ型熱電半導体材料を含む熱電半導体組成物を乾燥し、Ｐ型熱電素子層及びＮ型熱電素子層を得る工程である。例えば、図３（ｄ）においては、（ｃ）、（ｃ’）で得られた開口部１５に充填されたＰ型熱電半導体材料を含む熱電半導体組成物及びＮ型熱電半導体材料を含む熱電半導体組成物を乾燥し、Ｐ型熱電素子層１６ｂ、Ｎ型熱電素子層１６ａを形成する工程である。
乾燥方法としては、前述したように、熱風乾燥、熱ロール乾燥、赤外線照射等、従来公知の乾燥方法が採用できる。加熱温度は、通常、８０〜１５０℃であり、加熱時間は、加熱方法により異なるが、通常、数秒〜数十分であり、熱電半導体組成物の調製において溶媒を使用した場合、加熱温度は、使用した溶媒を乾燥できる温度範囲であれば、特に制限はない。
(Thermoelectric semiconductor composition drying step)
In the thermoelectric semiconductor composition drying step, the thermoelectric semiconductor composition containing the P-type thermoelectric semiconductor material and the thermoelectric semiconductor composition containing the N-type thermoelectric semiconductor material filled in the spaced openings are dried. This is a step of obtaining an element layer and an N-type thermoelectric element layer. For example, in FIG. 3D, a thermoelectric semiconductor composition including a P-type thermoelectric semiconductor material and a thermoelectric semiconductor including an N-type thermoelectric semiconductor material filled in the opening 15 obtained in (c) and (c ′). This is a step of drying the composition to form a P-type thermoelectric element layer 16b and an N-type thermoelectric element layer 16a.
As a drying method, a conventionally known drying method such as hot-air drying, hot-roll drying, and infrared irradiation can be employed as described above. The heating temperature is usually 80 to 150 ° C., and the heating time varies depending on the heating method, but is usually several seconds to several tens of minutes.When a solvent is used in the preparation of the thermoelectric semiconductor composition, the heating temperature is: There is no particular limitation as long as the solvent used can be dried.
〈アニール処理工程〉
本発明においては、Ｐ型熱電素子層及びＮ型熱電素子層をアニール処理する工程を含む。
アニール処理工程は、熱電半導体組成物乾燥工程において得られたＰ型熱電素子層及びＮ型熱電素子層を、熱処理する工程である。前述したように、アニール処理を行うことで、熱電性能を安定化させるとともに、熱電素子層の薄膜中の熱電半導体微粒子を結晶成長させることができ、熱電性能をさらに向上させることができる。また、アニール処理の条件は、前述したとおりである。
<Annealing process>
The present invention includes a step of annealing the P-type thermoelectric element layer and the N-type thermoelectric element layer.
The annealing treatment step is a step of heat-treating the P-type thermoelectric element layer and the N-type thermoelectric element layer obtained in the thermoelectric semiconductor composition drying step. As described above, by performing the annealing treatment, the thermoelectric performance can be stabilized, and the thermoelectric semiconductor particles in the thin film of the thermoelectric element layer can be crystal-grown, so that the thermoelectric performance can be further improved. The conditions of the annealing treatment are as described above.
（π型熱電変換素子製造工程）
π型熱電変換素子製造工程は、アニール処理工程で得られたＰ型熱電素子層及びＮ型熱電素子層を含む基板の熱電素子層側と対向基板上の電極とを対向させ、貼り合わせ、熱電変換素子とする工程である。例えば、図３（ｅ）においては、Ｎ型熱電素子層１６ａ及びＰ型熱電素子層１６ｂの上面側と基板１２ｂ上の電極１３ｂとを対向させ、接合材層（図示せず）等を介し、貼り合せることにより接合する工程である。この工程により、π型熱電変換素子が製造できる。
対向基板及び電極としては、前述した基板及び電極と同様のものを用いることができる。
前記接合材層に用いる接合材料としては、ハンダ材料、導電性接着剤、焼結接合剤等が挙げられ、それぞれ、ハンダ層、導電性接着剤層、焼結接合層として、電極上に形成されることが好ましい。
(Π-type thermoelectric conversion element manufacturing process)
In the π-type thermoelectric conversion element manufacturing process, the thermoelectric element layer side of the substrate including the P-type thermoelectric element layer and the N-type thermoelectric element layer obtained in the annealing step is opposed to the electrode on the opposing substrate, and the thermoelectric element is bonded. This is a step of forming a conversion element. For example, in FIG. 3E, the upper surface side of the N-type thermoelectric element layer 16a and the P-type thermoelectric element layer 16b and the electrode 13b on the substrate 12b are opposed to each other, with a bonding material layer (not shown) interposed therebetween. This is a step of bonding by bonding. By this step, a π-type thermoelectric conversion element can be manufactured.
As the counter substrate and the electrode, those similar to the aforementioned substrate and electrode can be used.
Examples of the bonding material used for the bonding material layer include a solder material, a conductive adhesive, a sintered bonding agent, and the like, and are formed on the electrode as a solder layer, a conductive adhesive layer, and a sintered bonding layer, respectively. Preferably.
本発明の熱電変換素子の製造方法によれば、簡便な方法で熱電素子層の形状制御性を向上させることができる。これにより、熱電変換素子の高集積化を実現することができる。 According to the method for manufacturing a thermoelectric conversion element of the present invention, the shape controllability of the thermoelectric element layer can be improved by a simple method. Thereby, high integration of the thermoelectric conversion element can be realized.
本発明の熱電変換素子及びその製造方法によれば、形状制御性が優れた熱電素子層を有する高集積化が可能な熱電変換素子を簡便な製造方法で得ることができる。また、同時に、複数の各Ｐ型熱電素子層−Ｎ型熱電素子層対の抵抗値のばらつきを小さくできることから、製造において歩留まりの向上が期待できる。
さらに、本発明の熱電変換素子は、屈曲性を有するとともに、薄型化（小型、軽量）が実現できる。
上記の熱電変換素子は熱電変換モジュールとすることにより、工場や廃棄物燃焼炉、セメント燃焼炉等の各種燃焼炉からの排熱、自動車の燃焼ガス排熱及び電子機器の排熱を電気に変換する発電用途に適用することが考えられる。冷却用途としては、エレクトロニクス機器の分野において、例えば、スマートフォン、各種コンピューター等に用いられるＣＰＵ（Ｃｅｎｔｒａｌ Ｐｒｏｃｅｓｓｉｎｇ Ｕｎｉｔ）、また、ＣＭＯＳ（Ｃｏｍｐｌｅｍｅｎｔａｒｙ Ｍｅｔａｌ Ｏｘｉｄｅ Ｓｅｍｉｃｏｎｄｕｃｔｏｒ Ｉｍａｇｅ Ｓｅｎｓｏｒ）、ＣＣＤ（Ｃｈａｒｇｅ Ｃｏｕｐｌｅｄ Ｄｅｖｉｃｅ）等のイメージセンサー、さらに、ＭＥＭＳ（Ｍｉｃｒｏ Ｅｌｅｃｔｒｏ Ｍｅｃｈａｎｉｃａｌ Ｓｙｓｔｅｍｓ）、その他の受光素子等の各種センサーの温度制御等に適用することが考えられる。
ADVANTAGE OF THE INVENTION According to the thermoelectric conversion element of this invention and its manufacturing method, the thermoelectric conversion element which can be highly integrated and has a thermoelectric element layer excellent in shape controllability can be obtained by a simple manufacturing method. At the same time, since the variation in the resistance value of each of the plurality of P-type thermoelectric element layers-N-type thermoelectric element layer pairs can be reduced, an improvement in yield in manufacturing can be expected.
Furthermore, the thermoelectric conversion element of the present invention has flexibility and can be made thin (small and light).
The above-mentioned thermoelectric conversion element is a thermoelectric conversion module, which converts exhaust heat from factories, waste combustion furnaces, cement combustion furnaces and other various types of combustion furnaces, automobile combustion gas exhaust heat, and electronic equipment exhaust heat to electricity. It is conceivable to apply to power generation applications. As a cooling application, in the field of electronic devices, for example, a CPU (Central Processing Unit) used for a smart phone, various computers, and the like, a CMOS (Complementary Metal Oxide Semiconductor Image Sensor), a CCD (Charge Coupled Image) sensor of a CCD (Charge Coupled), and the like. Further, the present invention can be applied to temperature control of various sensors such as MEMS (Micro Electro Mechanical Systems) and other light receiving elements.
１：熱電変換素子
２ａ，２ｂ：基板
３ａ，３ｂ：電極
４：パターン層
５：開口部
５ｓ：開口
６ａ：Ｎ型熱電素子層
６ｂ：Ｐ型熱電素子層
１２ａ，１２ｂ：基板
１３ａ，１３ｂ：電極
１４：パターン層
１４’：樹脂を含む層
１５：開口部
１５ｓ：開口
１６ａ：Ｎ型熱電素子層
１６ｂ：Ｐ型熱電素子層
1: thermoelectric conversion elements 2a, 2b: substrates 3a, 3b: electrode 4: pattern layer 5: opening 5s: opening 6a: N-type thermoelectric element layer 6b: P-type thermoelectric element layers 12a, 12b: substrates 13a, 13b: electrode 14: Pattern layer 14 ': Layer containing resin 15: Opening 15s: Opening 16a: N-type thermoelectric element layer 16b: P-type thermoelectric element layer
Claims (8)
前記パターン層が樹脂を含む層であり、前記Ｐ型熱電素子層及びＮ型熱電素子層が熱電半導体材料を含む熱電半導体組成物からなる、熱電変換素子。 A substrate having electrodes, a pattern layer having a plurality of spaced openings, a P-type thermoelectric element layer and an N-type thermoelectric element layer present in the spaced openings, and a thermoelectric conversion element including:
The thermoelectric conversion element, wherein the pattern layer is a layer containing a resin, and the P-type thermoelectric element layer and the N-type thermoelectric element layer are made of a thermoelectric semiconductor composition containing a thermoelectric semiconductor material.
前記パターン層が樹脂を含む層であり、前記Ｐ型熱電素子層及びＮ型熱電素子層が熱電半導体材料を含む熱電半導体組成物からなる、熱電変換素子の製造方法であって、
前記電極上に離間した開口部を有するパターン層を形成する工程、
前記離間した開口部にＰ型熱電半導体材料を含む熱電半導体組成物及びＮ型熱電半導体材料を含む熱電半導体組成物をそれぞれ充填する工程、
前記離間した開口部に充填された、前記Ｐ型熱電半導体材料を含む熱電半導体組成物及び前記Ｎ型熱電半導体材料を含む熱電半導体組成物を乾燥し、Ｐ型熱電素子層及びＮ型熱電素子層を得る工程、並びに
得られたＰ型熱電素子層及びＮ型熱電素子層をアニール処理する工程を含む、
熱電変換素子の製造方法。 A substrate having electrodes, a pattern layer having a plurality of spaced openings, and a P-type thermoelectric element layer and an N-type thermoelectric element layer in the spaced openings;
The method for manufacturing a thermoelectric conversion element, wherein the pattern layer is a layer containing a resin, and the P-type thermoelectric element layer and the N-type thermoelectric element layer are made of a thermoelectric semiconductor composition containing a thermoelectric semiconductor material.
Forming a pattern layer having openings spaced apart on the electrode,
Filling the separated openings with a thermoelectric semiconductor composition containing a P-type thermoelectric semiconductor material and a thermoelectric semiconductor composition containing an N-type thermoelectric semiconductor material, respectively;
The thermoelectric semiconductor composition containing the P-type thermoelectric semiconductor material and the thermoelectric semiconductor composition containing the N-type thermoelectric semiconductor material filled in the spaced openings are dried to form a P-type thermoelectric element layer and an N-type thermoelectric element layer. And annealing the obtained P-type and N-type thermoelectric element layers,
Manufacturing method of thermoelectric conversion element.
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| JP2002353523A (en) * | 2001-03-22 | 2002-12-06 | Ricoh Co Ltd | Thermoelectric conversion material, element thereof and manufacturing method therefor |
| JP2014007376A (en) * | 2012-05-30 | 2014-01-16 | Denso Corp | Thermoelectric conversion device |
| JP2017041540A (en) * | 2015-08-20 | 2017-02-23 | リンテック株式会社 | Peltier cooling element and method for manufacturing the same |
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