JP2009218310A - Thermal power generation device element - Google Patents

Thermal power generation device element Download PDF

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JP2009218310A
JP2009218310A JP2008058924A JP2008058924A JP2009218310A JP 2009218310 A JP2009218310 A JP 2009218310A JP 2008058924 A JP2008058924 A JP 2008058924A JP 2008058924 A JP2008058924 A JP 2008058924A JP 2009218310 A JP2009218310 A JP 2009218310A
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electrode
thermoelectric
power generation
ybal
metal layer
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JP5176609B2 (en
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Akihiro Sakai
章裕 酒井
Tsutomu Sugano
勉 菅野
Kohei Takahashi
宏平 高橋
Satoshi Yotsuhashi
聡史 四橋
Hideaki Adachi
秀明 足立
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Panasonic Corp
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermal power generation device element which has high power generation characteristics. <P>SOLUTION: The thermal power generation device element which includes a first electrode 11 and a second electrode 12, and a stack 13 formed by stacking an YbAl<SB>3</SB>layer 14 and a metal layer 15 alternately and electrically connected such that a direction 16 parallel to layers of the stack 13 is inclined to a direction 17 wherein the first electrode 11 and second electrode 12 are opposed to each other has high power generation characteristics by making a direction 18 wherein a temperature difference is applied perpendicular to the direction 17 wherein the electrodes are opposed to each other. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

本発明は熱エネルギーから電気エネルギーへの直接変換を行う熱発電デバイス素子に関する。   The present invention relates to a thermoelectric device element that performs direct conversion from thermal energy to electrical energy.

熱発電は、物質の両端に印加された温度差に比例して起電力が生じるゼーベック効果を利用し、熱エネルギーを直接電気エネルギーに変換する技術である。この技術は、僻地用電源、宇宙用電源、軍事用電源等で実用化されている。   Thermoelectric power generation is a technology that directly converts thermal energy into electrical energy using the Seebeck effect in which an electromotive force is generated in proportion to the temperature difference applied to both ends of a substance. This technology has been put to practical use in remote power supplies, space power supplies, military power supplies, and the like.

従来の熱発電デバイス素子は、キャリアの符号が異なるp型半導体とn型半導体を組み合わせ、熱的に並列に、かつ電気的に直列につないだ、いわゆるπ型構造と呼ばれる構成となっている。   A conventional thermoelectric power generation device element has a so-called π-type structure in which a p-type semiconductor and an n-type semiconductor having different carrier signs are combined and thermally connected in parallel and electrically in series.

熱電変換デバイスに用いられる熱電変換材料の性能は性能指数Zまたは絶対温度をかけて無次元化された性能指数ZTで評価される事が多い。ZTは、物質のS=ゼーベック係数、ρ=電気抵抗率、κ=熱伝導率、を用いて、ZT=S2T/ρκで記述される量である。また一方で、ゼーベック係数Sと電気抵抗率ρだけを考慮したS2/ρはパワーファクターと呼ばれ、温度差を一定とした場合の熱電材料の発電性能の良否を決定する基準となる。 The performance of the thermoelectric conversion material used for the thermoelectric conversion device is often evaluated by the figure of merit Z or the figure of merit ZT made dimensionless by applying an absolute temperature. ZT is a quantity described as ZT = S 2 T / ρκ, using S = Seebeck coefficient of the material, ρ = electric resistivity, κ = thermal conductivity. On the other hand, S 2 / ρ considering only the Seebeck coefficient S and the electric resistivity ρ is called a power factor, and is a standard for determining the quality of the thermoelectric material power generation performance when the temperature difference is constant.

現在、熱電変換材料として実用化されているBi2Te3は、ZTが1程度、パワーファクターが40〜50μW/cmK2であり、現状では比較的高い特性を持つが、それでも通常のπ型のデバイス構成にした場合には発電性能はあまり高くなく、より多くの用途での実用に足るほどには至っていない。 Bi 2 Te 3 currently in practical use as a thermoelectric conversion material has a ZT of about 1 and a power factor of 40 to 50 μW / cmK 2 , and has relatively high characteristics at present. In the case of a device configuration, the power generation performance is not so high, and it is not practical enough for more applications.

一方、π型以外のデバイス構成として、自然あるいは人工的に作られた積層構造における熱電気特性の異方性を利用したものが古くから提案されている(非特許文献1を参照)。しかし、非特許文献1によれば、このようなデバイスではZTの改善が見られないこと
から、熱発電用途ではなく、主に赤外線センサなど測定用途への応用が想定された開発が行われている。
On the other hand, as a device configuration other than the π-type, a device configuration utilizing the anisotropy of thermoelectric characteristics in a natural or artificial laminated structure has been proposed for a long time (see Non-Patent Document 1). However, according to Non-Patent Document 1, such a device does not show improvement in ZT, and therefore, development not intended for thermoelectric generation but mainly for measurement use such as an infrared sensor has been performed. Yes.

また、類似の構造を有するものとして、基板上にFeSi2系の熱電材料と、厚さが100nm以下のSiO2等の絶縁材料を、縞状に交互に配列させた熱電変換材料が特許文献1に開示されている。特許文献1によれば、このような微細構造を有する熱電材料は、主な構成材料であるFeSi2系材料の単独の特性と比較して、微細構造の効果でゼーベック係数が向上するものの、絶縁物質を含有するために導電率が低下する。すなわち電気抵抗率ρが増大するので、熱発電デバイス素子の内部抵抗の増大につながり、結果として負荷を通じて外部に取り出せる電力が小さくなってしまう。 Further, as a material having a similar structure, Patent Document 1 discloses a thermoelectric conversion material in which an FeSi 2 -based thermoelectric material and an insulating material such as SiO 2 having a thickness of 100 nm or less are alternately arranged in a stripe pattern on a substrate. Is disclosed. According to Patent Document 1, the thermoelectric material having such a fine structure has an improved insulating effect although the Seebeck coefficient is improved by the effect of the fine structure as compared with the single characteristic of the FeSi 2 -based material which is the main constituent material. Conductivity decreases due to the inclusion of substances. That is, since the electrical resistivity ρ increases, the internal resistance of the thermoelectric generator device element increases, and as a result, the electric power that can be extracted outside through the load decreases.

他に、積層構造を有する熱電材料としては、半金属、金属、または合成樹脂からなる層状体を備えた熱電材料が特許文献2に開示されている。これは、従来のいわゆるπ型のデバイス構成において、層状体の積層方向に温度差を印加し、同方向に対向するように配置された電極を介して電力を取り出す構成が適用対象となっており、本質的には非特許文献1に開示されているデバイス構成とは異なる。
特開平6−310766号公報 国際公開第00/076006号パンフレット THERMOELECTRICS HANDBOOK,Chapter 45,CRC Press(2006)
In addition, as a thermoelectric material having a laminated structure, Patent Document 2 discloses a thermoelectric material including a layered body made of a semimetal, a metal, or a synthetic resin. This applies to a conventional so-called π-type device configuration in which a temperature difference is applied in the laminating direction of the layered body and power is taken out via electrodes arranged so as to face each other in the same direction. Essentially, this is different from the device configuration disclosed in Non-Patent Document 1.
JP-A-6-310766 International Publication No. 00/076006 Pamphlet THERMOELECTRICS HANDBOOK, Chapter 45, CRC Press (2006)

前述の通り、従来の熱電デバイスでは、より多くの用途で実用に足るだけの十分な発電性能を得ることができない。本発明者等は実用的な性能を持つ熱電変換デバイス実現のため、積層体を有するデバイス構成に関して鋭意研究を重ねてきた結果、金属とYbAl3からなる積層体の、層方向を電極の対向方向に対して傾斜させたデバイスにおいて、YbAl3単独と比較して電気抵抗率が抑制され、かつ発電特性が大幅に向上するという意外な知見を見出し、この知見に基づいて本デバイスの発明に至った。 As described above, the conventional thermoelectric device cannot obtain sufficient power generation performance sufficient for practical use in more applications. As a result of intensive studies on a device structure having a laminated body in order to realize a thermoelectric conversion device having practical performance, the present inventors have determined that the layer direction of the laminated body composed of metal and YbAl 3 is the opposite direction of the electrode. As a result, the inventors found an unexpected finding that the electrical resistivity is suppressed and the power generation characteristics are greatly improved as compared with YbAl 3 alone, and the invention of the present device has been reached based on this finding. .

前記従来の課題を解決するために、本発明の熱発電デバイス素子は、第1電極および第2電極と、YbAl3と金属が交互に積層されてなる積層体とからなり、前記第1電極および第2電極の対向方向に対して該積層体の層の向きが傾斜するよう電気的に接続され、前記電極の対向方向に対して垂直方向に温度差を印加するような配置を取るように構成される。 In order to solve the conventional problem, the thermoelectric device element of the present invention includes a first electrode and a second electrode, and a laminate in which YbAl 3 and a metal are alternately laminated, and the first electrode and It is electrically connected so that the direction of the layer of the laminated body is inclined with respect to the opposing direction of the second electrode, and is arranged to apply a temperature difference in a direction perpendicular to the opposing direction of the electrode Is done.

本発明の熱発電デバイス素子によれば、積層体を構成する金属およびYbAl3の厚さの比および積層体の層の向きと電極の対向方向とがなす傾斜角度を適切に選択することで構成材料単独の性能を大きく超える高い発電特性が得られる。これにより従来の性能を超える熱発電が可能となり、実用的な熱発電デバイス素子が実現する。すなわち熱と電気とのエネルギー変換の応用を促進させるものであり、本発明の工業的価値は高い。 According to the thermoelectric device element of the present invention, the thickness ratio of the metal constituting the laminate and YbAl 3 and the inclination angle formed by the direction of the layers of the laminate and the opposing direction of the electrodes are appropriately selected. High power generation characteristics that greatly exceed the performance of the material alone can be obtained. As a result, thermoelectric power generation exceeding the conventional performance becomes possible, and a practical thermoelectric power generation device element is realized. That is, it promotes the application of energy conversion between heat and electricity, and the industrial value of the present invention is high.

以下本発明の実施の形態について、図面を参照しながら説明する。   Embodiments of the present invention will be described below with reference to the drawings.

(実施の形態1)
図1は、本発明の実施の形態1における熱発電デバイス素子の構成を示した図である。
(Embodiment 1)
FIG. 1 is a diagram showing a configuration of a thermoelectric device element according to Embodiment 1 of the present invention.

図1において、平行に配置された第1電極11と第2電極12によって積層体13を挟んだような構成で熱発電デバイス素子が形成されている。積層体13はYbAl3層14と金属層15が交互に積層されて構成され、その層に平行な方向16は電極の対向方向17に対して角度θだけ傾斜している。 In FIG. 1, a thermoelectric device element is formed in such a configuration that a laminated body 13 is sandwiched between a first electrode 11 and a second electrode 12 that are arranged in parallel. The laminate 13 is configured by alternately laminating YbAl 3 layers 14 and metal layers 15, and a direction 16 parallel to the layers is inclined by an angle θ with respect to the opposing direction 17 of the electrodes.

このように構成された熱発電デバイス素子を駆動する際に温度差を印加する、すなわち温度勾配が生じる方向18は電極の対向方向17に対して直交しており、発生した電力は第1電極11と第2電極12を介して取り出される。具体的には図2に示したように、熱発電デバイス素子21の電極を配置しない一方の面に高温部22を、他方の面に低温部23を密着させて熱発電デバイス素子に対して温度差を印加する。この構成において、温度勾配が生じる方向24は図2に示したように電極の対向方向に対して垂直となる。   A temperature difference is applied when driving the thermoelectric device element configured as described above, that is, the direction 18 in which the temperature gradient is generated is orthogonal to the opposing direction 17 of the electrode, and the generated power is the first electrode 11. And taken out via the second electrode 12. Specifically, as shown in FIG. 2, the temperature of the thermoelectric device element is set so that the high temperature portion 22 is in close contact with the one surface where the electrode of the thermoelectric device element 21 is not disposed and the low temperature portion 23 is in close contact with the other surface. Apply the difference. In this configuration, the direction 24 in which the temperature gradient occurs is perpendicular to the facing direction of the electrodes as shown in FIG.

π型構造を有する従来の熱発電デバイス素子では、温度差を印加する方向に対して平行方向だけに起電力が生じ、垂直方向に起電力が生じることは無い。詳細は後述する実施例で述べるが、本発明者等は様々な条件を検討し最適化することにより、積層体13の層に平行な方向16と電極の対向方向17とがなす角度、およびYbAl3層14と金属層15の厚さおよびその比と熱発電性能の関係を詳細に調べて行く過程で、上記条件を適切に設定することにより本発明の熱発電デバイス素子において予想外に大きな熱発電性能が得られることを見出した。 In a conventional thermoelectric generator device element having a π-type structure, an electromotive force is generated only in the direction parallel to the direction in which the temperature difference is applied, and no electromotive force is generated in the vertical direction. Although details will be described in the examples described later, the present inventors have examined and optimized various conditions, and thereby, the angle formed between the direction 16 parallel to the layer of the laminated body 13 and the facing direction 17 of the electrode, and YbAl In the process of investigating in detail the relationship between the thickness of the three layers 14 and the metal layer 15 and the ratio thereof and the thermoelectric generation performance, an unexpectedly large heat is generated in the thermoelectric device element of the present invention by appropriately setting the above conditions. It was found that power generation performance can be obtained.

本発明の熱発電デバイス素子における第1電極11および第2電極12は電気伝導の良い材料であれば特に限定されない。具体的にはCu、Ag、Mo、W、Al、Ti、Cr、Au、Pt、In等の金属またはTiN、スズ添加酸化インジウム(ITO)、SnO2等の窒化物または酸化物が良い。また、はんだや導電性ペーストを用いることもできる。 The 1st electrode 11 and the 2nd electrode 12 in the thermoelectric device element of this invention will not be specifically limited if it is a material with good electrical conductivity. Specifically, a metal such as Cu, Ag, Mo, W, Al, Ti, Cr, Au, Pt, or In or a nitride or oxide such as TiN, tin-added indium oxide (ITO), or SnO 2 is preferable. Also, solder or conductive paste can be used.

積層体13を構成する金属層15は熱伝導率κが高く、かつ電気抵抗率が小さいものが良い。具体的にはCu、Ag、Auあるいはこれらの材料からなる合金であるが、特にCuとAgが好ましい。   The metal layer 15 constituting the laminate 13 preferably has a high thermal conductivity κ and a low electrical resistivity. Specifically, Cu, Ag, Au, or an alloy made of these materials is used, and Cu and Ag are particularly preferable.

本発明の熱発電デバイス素子の作製方法を、図3を参照しながら説明する。積層体13を構成する積層構造体は、例えば金属32の箔にYbAl3層14を堆積したものを交互に重ねて圧力をかけ、またさらに熱も加えて圧着成形して作製することができる。 A method for producing the thermoelectric device element of the present invention will be described with reference to FIG. The laminated structure constituting the laminated body 13 can be produced by, for example, alternately laminating a metal 32 foil with the YbAl 3 layer 14 deposited thereon, applying pressure, and further applying heat and pressure forming.

次に、以上のようにして作製した積層構造体を切り出し、板状の積層体13に加工する。この際、図3の破線に示したように積層の向きが板状の積層体13の表面に対して所望の傾斜角度となるよう、切り出し範囲33を設定する。必要があれば切り出した積層体13に研磨処理を行っても良い。その後、板状の積層体13の、傾斜方向の一対の端面の一部あるいは全面に第1電極11および第2電極12を設けることにより、本発明の熱発電デバイス素子を得ることができる。   Next, the laminated structure produced as described above is cut out and processed into a plate-like laminated body 13. At this time, the cutout range 33 is set so that the stacking direction becomes a desired inclination angle with respect to the surface of the plate-shaped stacked body 13 as shown by the broken line in FIG. If necessary, the laminated body 13 cut out may be polished. Then, the thermoelectric device element of the present invention can be obtained by providing the first electrode 11 and the second electrode 12 on a part or the entire surface of the pair of end surfaces in the inclined direction of the plate-like laminate 13.

本デバイスを構成する積層体13における金属層15とYbAl3層14の厚みの比は97:3から50:50の範囲にあることが好ましい。この理由は、後述する実施例2からも理解されるように、この範囲外であると、パワーファクター(S2/ρ)の値が十分大きくならないからである。また、積層体13の層に平行な方向16と電極の対向方向17とがなす角度θは20°から60°の範囲にあるように作製することが好ましく30°から50°であることがより好ましい。この理由は、後述する実施例1からも理解されるように、20°未満または60°を超えると、パワーファクター(S2/ρ)の値が十分大きくならないからである。 The thickness ratio of the metal layer 15 and the YbAl 3 layer 14 in the laminate 13 constituting the device is preferably in the range of 97: 3 to 50:50. This is because the power factor (S 2 / ρ) does not become sufficiently large outside this range, as will be understood from Example 2 described later. Further, the angle θ formed by the direction 16 parallel to the layers of the laminate 13 and the facing direction 17 of the electrode is preferably in the range of 20 ° to 60 °, more preferably 30 ° to 50 °. preferable. This is because the value of the power factor (S 2 / ρ) is not sufficiently increased when the angle is less than 20 ° or exceeds 60 °, as will be understood from Example 1 described later.

金属層15を基体としてYbAl3層14の薄膜を作製する際の作製方法は特に限定されないので、スパッタ法、蒸着法、レーザーアブレーション法、化学的気相成長法などの気相成長によるもの、ゾルゲル法などによる溶液から薄膜を作成する方法やバルク体を研磨して薄くする方法などが適用可能である。 The production method for producing the thin film of the YbAl 3 layer 14 using the metal layer 15 as a base is not particularly limited, so that it is based on vapor phase growth such as sputtering, vapor deposition, laser ablation, chemical vapor deposition, sol gel A method of forming a thin film from a solution by a method or a method of polishing and thinning a bulk body can be applied.

第1電極11および第2電極12の作製方法は、蒸着法、スパッタ法などの気相成長の他に、導電性ペーストの塗布、めっき、溶射、はんだによる接合など様々な方法を用いることができる。   As a method for manufacturing the first electrode 11 and the second electrode 12, various methods such as coating of conductive paste, plating, thermal spraying, and joining by soldering can be used in addition to vapor deposition such as vapor deposition and sputtering. .

(実施の形態2)
図4は本発明の実施の形態2における熱発電デバイスの構成を示した図である。
図4で示したのは、実施の形態1と同様の手順で作製される板状の積層体を、接続電極43を介して電気的に接続して平板状に構成したものである。このように構成される熱発電デバイスを用いて適用面積を大きくすることにより、全体としてより多くの発電量を得ることができる。
(Embodiment 2)
FIG. 4 is a diagram showing the configuration of the thermoelectric generator device according to Embodiment 2 of the present invention.
In FIG. 4, a plate-like laminate manufactured in the same procedure as in the first embodiment is electrically connected via a connection electrode 43 to form a flat plate. By increasing the application area using the thermoelectric power generation device configured as described above, a larger amount of power generation can be obtained as a whole.

本デバイスにおける接続電極43は電気伝導の良い材料であれば特に限定されない。具体的にはCu、Ag、Mo、W、Al、Ti、Cr、Au、Pt、In等の金属またはTiN、スズ添加酸化インジウム(ITO)、SnO2等の窒化物や酸化物が良い。また、はんだや導電性ペーストを用いることも可能である。作製方法は、蒸着法、スパッタ法などの気相成長の他にめっき、溶射など様々な方法を用いることができる。 The connection electrode 43 in this device is not particularly limited as long as it is a material having good electrical conductivity. Specifically, metals such as Cu, Ag, Mo, W, Al, Ti, Cr, Au, Pt, and In, or nitrides and oxides such as TiN, tin-added indium oxide (ITO), and SnO 2 are preferable. Also, solder or conductive paste can be used. As a manufacturing method, various methods such as plating and thermal spraying can be used in addition to vapor deposition such as vapor deposition and sputtering.

このようにして作製される熱発電デバイスを駆動する際は、平板状のデバイスの一方の
面に高温部、他方の面に低温部を密着して熱流を生じさせることによって温度差を印加する。熱流から本デバイスによって変換された電力は取り出し電極44を介して外部に取り出すことができる。
When driving the thermoelectric power generation device manufactured in this way, a temperature difference is applied by causing a high temperature part to adhere to one surface of the flat device and a low temperature part to the other surface to generate a heat flow. The electric power converted by the device from the heat flow can be extracted outside through the extraction electrode 44.

本実施の形態における熱発電デバイスを構成するにあたり、積層体は接続電極43を介して電気的に直列に接続する他に、図5に示すように電気的に並列に接続しても良い。積層体を直列に接続する利点は、電力を取り出す際の電圧を大きくすることにある。積層体を並列に接続すると、熱発電デバイス全体の内部抵抗を小さくすることの他に、接続電極43による電気的な接続が一部断線してもデバイス全体としての電気的な接続を保つことにも利点がある。すなわち、これら直列および並列接続を適切に組み合わせる(例えば、図5を参照)ことによって、高い発電能力を有する熱発電デバイスを構成することができる。   In configuring the thermoelectric power generation device in the present embodiment, the laminates may be electrically connected in parallel as shown in FIG. 5 in addition to being electrically connected in series via the connection electrode 43. The advantage of connecting the stacked bodies in series is to increase the voltage when extracting power. When the stacked bodies are connected in parallel, in addition to reducing the internal resistance of the entire thermoelectric power generation device, the electrical connection of the entire device is maintained even if the electrical connection by the connection electrode 43 is partially broken. There are also advantages. That is, by appropriately combining these series and parallel connections (see, for example, FIG. 5), a thermoelectric power generation device having a high power generation capability can be configured.

(実施例)
以下、本発明のより具体的な実施例を説明する。
(Example)
Hereinafter, more specific examples of the present invention will be described.

(実施例1)
YbAl3層14と金属の積層体13として、幾つかの金属材料を用いて本発明の熱発電デバイス素子を作製した。金属とYbAl3の積層体は、図3に示すように、金属箔の両面にYbAl3薄膜を形成して得られたYbAl3/金属箔/YbAl3のシートを重ね合わせて加熱しながら圧着することにより作製した。第1電極11および第2電極12にはAuを用いた。
Example 1
As the YbAl 3 layer 14 and the metal laminate 13, thermoelectric device elements of the present invention were manufactured using several metal materials. As shown in FIG. 3, the laminate of metal and YbAl 3 is bonded with heat while superposing sheets of YbAl 3 / metal foil / YbAl 3 obtained by forming YbAl 3 thin films on both sides of the metal foil. This was produced. Au was used for the first electrode 11 and the second electrode 12.

まず100mm×100mm、厚さ90μmの金属箔の両面にRFマグネトロンスパッタリング法により膜厚5μmのYbAl3からなる薄膜を両面に形成した。スパッタリングを行う際にはスパッタリングターゲットとしてYb−Alの焼結体を用い、具体的な作成条件としてはスパッタリング電力を100W、スパッタリングガスおよび雰囲気圧力をそれぞれアルゴン、0.5Paに設定して常温において金属箔上にYbAl3の堆積を行った。 First, a thin film made of YbAl 3 having a film thickness of 5 μm was formed on both surfaces of a metal foil having a size of 100 mm × 100 mm and a thickness of 90 μm by RF magnetron sputtering. When sputtering, a Yb-Al sintered body is used as a sputtering target. Specific production conditions include sputtering power of 100 W, sputtering gas and atmospheric pressure of argon and 0.5 Pa, respectively, and metal at room temperature. YbAl 3 was deposited on the foil.

金属とYbAl3の積層体を形成後、5mm×50mmの大きさに切断して短冊状の小片を得た。金属箔としては、金、銀、銅の各種金属材料の素材の箔を用いた。同様の工程を繰り返した後、この小片を200枚重ね合わせ、積層方向に100kg/cm2の荷重をかけながら10-4Paの減圧下において650℃で30分間の加熱を行い、各小片の圧着を行った。圧着後、おおよそ5mm×50mm×20mmの積層構造体を得た。この積層構造体に対して、切削研磨を行い、3mm×48mm×20mmの積層構造体を得た。積層断面を走査電子顕微鏡にて観察したところ、金属層が約90μm、が約10μmの厚さで周期的に積層しているのを確認した。またエネルギー分散型X線元素分析をYbAl3層において行ったところ、Yb:Al=1:3であることが判明した。 After forming a laminate of metal and YbAl 3 , it was cut into a size of 5 mm × 50 mm to obtain a strip-shaped piece. As the metal foil, a foil made of various metal materials such as gold, silver and copper was used. After repeating the same process, 200 pieces of these small pieces were superposed and heated at 650 ° C. for 30 minutes under a reduced pressure of 10 −4 Pa while applying a load of 100 kg / cm 2 in the stacking direction. Went. After crimping, a laminated structure of approximately 5 mm × 50 mm × 20 mm was obtained. The laminated structure was cut and polished to obtain a laminated structure of 3 mm × 48 mm × 20 mm. When the laminated cross section was observed with a scanning electron microscope, it was confirmed that the metal layers were periodically laminated with a thickness of about 90 μm and a thickness of about 10 μm. Further, when energy dispersive X-ray elemental analysis was performed on the YbAl 3 layer, it was found that Yb: Al = 1: 3.

こうして得られた積層構造体に対して、ダイヤモンドカッターを用いた切削加工で積層周期に対して図3に示したように10°間隔の角度で傾斜をつけて平板状に切り出した。平板の厚みは1mmとし、幅3mmで長さ20mmの平板を0°から90°までの範囲の各傾斜角度(θ)に対して作製した。その後スパッタ法により長辺の両端にAuからなる電極を形成し、図1に示したような構造のデバイスを作製した。作製した試料に対して発電性能の評価を行った。図2に示すように平板デバイスの片側をヒータで150℃に加熱し、もう片側を水冷で30℃に冷却して端子間の起電圧と電気抵抗を測定した。銀箔を用いて40°傾斜させたデバイスの場合、起電圧67mVで抵抗は0.27mΩであった。これよりパワーファクターは190μW/cmK2と見積もられた。同様の手順で、各金属材料を用いた傾斜角度の異なるデバイスの性能を測定したところ、表1の結果となった。 The laminated structure thus obtained was cut into a flat plate with an inclination of 10 ° intervals as shown in FIG. 3 by cutting using a diamond cutter as shown in FIG. The thickness of the flat plate was 1 mm, and a flat plate having a width of 3 mm and a length of 20 mm was prepared for each inclination angle (θ) in the range from 0 ° to 90 °. Thereafter, electrodes made of Au were formed on both ends of the long side by sputtering, and a device having a structure as shown in FIG. 1 was produced. The power generation performance was evaluated for the prepared samples. As shown in FIG. 2, one side of the flat plate device was heated to 150 ° C. with a heater, the other side was cooled to 30 ° C. with water cooling, and the electromotive voltage and electrical resistance between the terminals were measured. In the case of a device tilted 40 ° using silver foil, the electromotive force was 67 mV and the resistance was 0.27 mΩ. From this, the power factor was estimated to be 190 μW / cmK 2 . When the performance of devices having different inclination angles using each metal material was measured in the same procedure, the results shown in Table 1 were obtained.

以上の結果から、各金属材料に関してほぼ共通に傾斜角度が20°〜60°の時に、現在実用化されているBi2Te3を用いた素子の2倍程度以上の優れたデバイス特性が得られることが判った。特に金属材料として、銀あるいは銅を用いた場合、他の金属に比べて性能が高いことが確認された。 From the above results, when the inclination angle is 20 ° to 60 ° almost in common with each metal material, it is possible to obtain excellent device characteristics more than twice that of an element using Bi 2 Te 3 which is currently in practical use. I found out. In particular, when silver or copper was used as the metal material, it was confirmed that the performance was higher than that of other metals.

Figure 2009218310
Figure 2009218310

(実施例2)
実施例1と同様の手法で、銀と銅の金属材料を用いて金属の厚みの異なる積層デバイスを構成した。傾斜角度は40°に固定し、金属箔の厚みを25μm、35μm、45μm、47.5μm、48.5μmと変化させて全体の積層周期が50μmとなるYbAl3との積層構造を作製した。この際のYbAl3の割合はそれぞれ50%、30%、10%、5%、3%である。
(Example 2)
In the same manner as in Example 1, laminated devices having different metal thicknesses were configured using silver and copper metal materials. The tilt angle was fixed at 40 °, and the thickness of the metal foil was changed to 25 μm, 35 μm, 45 μm, 47.5 μm, and 48.5 μm, and a laminated structure with YbAl 3 having a total lamination period of 50 μm was produced. In this case, the proportions of YbAl 3 are 50%, 30%, 10%, 5%, and 3%, respectively.

40°の平板状に切り出して作製した厚み1mm、幅3mm、長さ20mmの熱発電デバイス素子のパワーファクターの測定結果は表2のようになった。YbAl3の厚みの比により性能が左右され、10%付近で最も良い性能であることが確認された。またこの傾向は銀についても銅についても同じ傾向であった。 Table 2 shows the measurement results of the power factor of a thermoelectric device element having a thickness of 1 mm, a width of 3 mm, and a length of 20 mm produced by cutting into a 40 ° flat plate. The performance was influenced by the thickness ratio of YbAl 3 , and it was confirmed that the performance was the best around 10%. This tendency was the same for silver and copper.

Figure 2009218310
Figure 2009218310

(実施例3)
金属箔として20μmの銅箔を用い、実施例1と同様の手法で積層デバイスを構成した。20μmのCu箔の両面に、YbAl3薄膜を0.3μmから10μmまで膜厚変化させて形成、加熱圧着し、その結果YbAl3層厚が0.6μm、1μm、2μm、6μm、20μmのCu/YbAl3積層構造を作製した。切り出し角度を20°から60°まで10°ごとに設定してデバイスを作製し、パワーファクターを測定したところ、表3の結果が得られた。
Example 3
A laminated device was constructed in the same manner as in Example 1 using a 20 μm copper foil as the metal foil. A YbAl 3 thin film is formed on both sides of a 20 μm Cu foil while changing the film thickness from 0.3 μm to 10 μm, and thermocompression bonded. As a result, the YbAl 3 layer thickness is 0.6 μm, 1 μm, 2 μm, 6 μm, 20 μm Cu / A YbAl 3 laminated structure was produced. A device was produced by setting the cut-out angle from 20 ° to 60 ° every 10 °, and the power factor was measured. The results shown in Table 3 were obtained.

Figure 2009218310
Figure 2009218310

この結果、YbAl3層厚に関して0.6μmから20μmの範囲で優れたデバイス性能が得られたことが確認された。これは全体の積層周期におけるCu:YbAl3の比が97:3から50:50の範囲にある時に好ましい結果となることを示したものであり、特に10:1(YbAl3層の割合が約10%)近傍の時に最も優れた性能が得られている。 As a result, it was confirmed that excellent device performance was obtained in the range of 0.6 μm to 20 μm with respect to the YbAl 3 layer thickness. This indicates that a favorable result is obtained when the ratio of Cu: YbAl 3 in the entire stacking period is in the range of 97: 3 to 50:50, especially 10: 1 (the ratio of the YbAl 3 layer is about 10%), the best performance is obtained.

この結果と実施例2の結果と併せて考えると、積層デバイスの性能は金属層の厚みやYbAl3層の厚みの絶対値に依るのではなく、全体の積層周期におけるYbAl3層の厚みの割合に依存していることが判る。また傾斜角度に関しては、20°から60°の範囲の中でも特に30〜40°の際に150μW/cmK2を超えることが確認され、現在実用化されているBi2Te3用いた素子の3倍程度以上の高性能熱発電デバイス素子が実現した。 Considering this result together with the result of Example 2, the performance of the laminated device does not depend on the absolute value of the thickness of the metal layer or the thickness of the YbAl 3 layer, but the ratio of the thickness of the YbAl 3 layer in the entire lamination cycle. It turns out that it depends on. In addition, the tilt angle is confirmed to exceed 150 μW / cmK 2 in the range of 20 ° to 60 °, particularly 30 to 40 °, and is three times as large as the device using Bi 2 Te 3 which is currently in practical use. A high-performance thermoelectric device element of a degree higher than that was realized.

(実施例4)
実装面積をより広くし、さらに多くの発電量を得るために、金属42、接続電極43、取り出し電極44としてCuを用いた、図4に示したような熱発電デバイスを作製した。
Example 4
In order to increase the mounting area and obtain a larger amount of power generation, a thermoelectric power generation device as shown in FIG. 4 using Cu as the metal 42, the connection electrode 43, and the extraction electrode 44 was produced.

CuとYbAl3からなる積層体は実施例1と同様の手順で作製した。Cuが20μm厚でYbAl3が1μm厚、すなわちCuとYbAl3の積層方向の厚さの比が10:1になるように積層体を構成し、かつ傾斜角は40°とした。積層体の寸法は長さ50mm×幅3mm×厚さ0.5mmとしたものを合計15個作製した。また、接続電極43および取り出し電極44のCuは厚さ0.5mmの板を使用した。 A laminate made of Cu and YbAl 3 was produced in the same procedure as in Example 1. The laminate was configured such that Cu was 20 μm thick and YbAl 3 was 1 μm thick, that is, the thickness ratio of Cu and YbAl 3 in the stacking direction was 10: 1, and the tilt angle was 40 °. A total of 15 laminates with a length of 50 mm, a width of 3 mm, and a thickness of 0.5 mm were produced. In addition, a plate having a thickness of 0.5 mm was used as Cu for the connection electrode 43 and the extraction electrode 44.

作製した15個の積層体をアルミナからなる支持体46上に1mm間隔で配列し、接続電極43および取り出し電極44は銀ペーストを用いて電気的に直列接続した。この際、熱流による起電力が相殺されないよう、図4に示したように隣り合う積層体の傾斜構造は互いに逆向きになるように配置し、約60mm×60mmの熱発電デバイスを作製した。取り出し電極44間の抵抗値を測定したところ、1.3mΩであった。   Fifteen prepared laminates were arranged on a support 46 made of alumina at an interval of 1 mm, and the connection electrode 43 and the extraction electrode 44 were electrically connected in series using a silver paste. At this time, in order not to cancel the electromotive force due to the heat flow, the inclined structures of the adjacent laminated bodies were arranged so as to be opposite to each other as shown in FIG. 4, and a thermoelectric power generation device of about 60 mm × 60 mm was manufactured. When the resistance value between the extraction electrodes 44 was measured, it was 1.3 mΩ.

以上の手順で作製した本実施例の熱発電デバイスの発電特性を評価した。支持体46を裏面から水冷し、低温部とした。本デバイスの他方の面に高温部となるセラミックヒータ
ーを密着させた。このような構成で低温部を25℃、高温部を40℃に保持したところ、開放端起電力は0.3Vとなり、パワーファクターを見積もると177μW/cmK2という高い値が得られた。この結果、本デバイスから最大3Wの電力を取り出すことができた。
The power generation characteristics of the thermoelectric power generation device of this example produced by the above procedure were evaluated. The support 46 was cooled with water from the back surface to form a low temperature part. A ceramic heater serving as a high temperature part was adhered to the other surface of the device. When the low temperature part was kept at 25 ° C. and the high temperature part was kept at 40 ° C. with such a configuration, the open end electromotive force was 0.3 V, and a high value of 177 μW / cm K 2 was obtained when the power factor was estimated. As a result, a maximum of 3 W of power could be extracted from this device.

本発明にかかる熱発電デバイス素子は、優れた発電特性を有しており、自動車や工場から排出される排ガスなどの熱を用いた発電機として利用可能である。   The thermoelectric power generation device element according to the present invention has excellent power generation characteristics and can be used as a power generator using heat such as exhaust gas discharged from an automobile or a factory.

また、小型の携帯発電機などの用途にも応用できる。   It can also be applied to small portable generators.

本発明の実施の形態1における熱発電デバイス素子の構成を示した図The figure which showed the structure of the thermoelectric-power generation device element in Embodiment 1 of this invention 本発明の実施の形態1における熱発電デバイス素子を駆動する際の構成を示した図The figure which showed the structure at the time of driving the thermoelectric generation device element in Embodiment 1 of this invention 本発明の実施の形態1における積層構造体に切削加工を行う際の切り出し範囲の例を示した図The figure which showed the example of the cut-out range at the time of cutting to the laminated structure in Embodiment 1 of this invention 本発明の実施の形態2における熱発電デバイスの構成を示した図The figure which showed the structure of the thermoelectric power generation device in Embodiment 2 of this invention 本発明の実施の形態2における熱発電デバイスの構成を示した図The figure which showed the structure of the thermoelectric power generation device in Embodiment 2 of this invention

符号の説明Explanation of symbols

11 第1電極
12 第2電極
13 積層体
14 YbAl3
15 金属層
16 層に平行な方向
17 電極の対向方向
18 温度勾配が生じる方向
21 熱発電デバイス素子
22 高温部
23 低温部
24 温度勾配が生じる方向
31 YbAl3
32 金属
33 切り出し範囲
41 YbAl3
42 金属
43 接続電極
44 取り出し電極
45 支持体
DESCRIPTION OF SYMBOLS 11 1st electrode 12 2nd electrode 13 Laminated body 14 YbAl 3 layer 15 Metal layer 16 Direction parallel to the layer 17 Opposite direction of electrode 18 Direction in which temperature gradient occurs 21 Thermoelectric device element 22 High temperature portion 23 Low temperature portion 24 Temperature gradient Direction of occurrence 31 YbAl 3
32 Metal 33 Cutting range 41 YbAl 3
42 Metal 43 Connection electrode 44 Extraction electrode 45 Support

Claims (21)

第1電極と、
前記第1電極に対向する第2電極と、
前記第1電極および前記第2電極との間に挟まれ、かつ前記第1電極および前記第2電極のいずれにも電気的に接続された積層体とを具備し、
前記積層体は、YbAl3層と金属層とが交互に積層されてなり、
前記YbAl3層および前記金属層が、前記第1電極と前記第2電極とが対向する方向に対して傾斜しており、
前記対向する方向に対して垂直方向に温度差を印加することによって、前記第1電極および前記第2電極をと介して電力を取り出す、熱発電デバイス素子。
A first electrode;
A second electrode facing the first electrode;
A laminated body sandwiched between the first electrode and the second electrode and electrically connected to both the first electrode and the second electrode;
The laminate is formed by alternately laminating YbAl 3 layers and metal layers,
The YbAl 3 layer and the metal layer are inclined with respect to a direction in which the first electrode and the second electrode face each other;
A thermoelectric device element that takes out electric power through the first electrode and the second electrode by applying a temperature difference in a direction perpendicular to the opposing direction.
前記YbAl3層および前記金属層が、前記第1電極と前記第2電極とが対向する方向に対して角度θで傾斜しており、
前記角度θが20°以上60°以下である、
請求項1に記載の熱発電デバイス素子。
The YbAl 3 layer and the metal layer are inclined at an angle θ with respect to a direction in which the first electrode and the second electrode face each other;
The angle θ is 20 ° or more and 60 ° or less,
The thermoelectric power generation device element according to claim 1.
前記角度θが30°以上50°以下である、
請求項2に記載の熱発電デバイス素子。
The angle θ is 30 ° or more and 50 ° or less,
The thermoelectric power generation device element according to claim 2.
前記金属層がCu、Ag、またはAuからなる、
請求項1に記載の熱発電デバイス素子。
The metal layer is made of Cu, Ag, or Au;
The thermoelectric power generation device element according to claim 1.
前記金属層が、CuまたはAgからなる、
請求項4に記載の熱発電デバイス素子。
The metal layer is made of Cu or Ag;
The thermoelectric power generation device element according to claim 4.
前記金属層の厚み:前記YbAl3層の厚みの比が97:3から50:50までの範囲内にある、
請求項1に記載の熱発電デバイス素子。
The ratio of the thickness of the metal layer to the thickness of the YbAl 3 layer is in the range of 97: 3 to 50:50.
The thermoelectric power generation device element according to claim 1.
前記金属層の厚み:前記YbAl3層の厚みの比が95:5から90:10までの範囲内にある、
請求項6に記載の熱発電デバイス素子。
The ratio of the thickness of the metal layer to the thickness of the YbAl 3 layer is in the range of 95: 5 to 90:10.
The thermoelectric power generation device element according to claim 6.
前記金属層がCu、Ag、またはAuからなり、
前記金属層の厚み:前記YbAl3層の厚みの比が97:3から50:50までの範囲内にある、
請求項2に記載の熱発電デバイス素子。
The metal layer is made of Cu, Ag, or Au;
The ratio of the thickness of the metal layer to the thickness of the YbAl 3 layer is in the range of 97: 3 to 50:50.
The thermoelectric power generation device element according to claim 2.
前記金属層が、CuまたはAgからなり、
前記金属層の厚み:前記YbAl3層の厚みの比が95:5から90:10までの範囲内にある、
請求項3に記載の熱発電デバイス素子。
The metal layer is made of Cu or Ag;
The ratio of the thickness of the metal layer to the thickness of the YbAl 3 layer is in the range of 95: 5 to 90:10.
The thermoelectric power generation device element according to claim 3.
第1電極と、
前記第1電極に対向する第2電極と、
前記第1電極および前記第2電極との間に挟まれ、かつ前記第1電極および前記第2電極のいずれにも電気的に接続された積層体と
を具備し、
前記積層体は、YbAl3層と金属層とが交互に積層されてなり、
前記YbAl3層および前記金属層が、前記第1電極と前記第2電極とが対向する方向に対して傾斜しており、
前記対向する方向に対して垂直方向に温度差を印加することによって、前記第1電極および前記第2電極をと介して電力を取り出す、熱発電デバイス素子の製造方法であって、
前記製造方法は、以下の工程を有する:
YbAl3層と金属層とを交互に積層してなる積層構造体を得る積層構造体形成工程、
前記積層構造体の積層方向に対して傾斜する面で前記積層構造体を切り出して前記積層体を得る積層体切り出し工程、
前記積層体に前記第1電極および前記第2電極を形成する電極形成工程。
A first electrode;
A second electrode facing the first electrode;
A laminated body sandwiched between the first electrode and the second electrode and electrically connected to both the first electrode and the second electrode;
The laminate is formed by alternately laminating YbAl 3 layers and metal layers,
The YbAl 3 layer and the metal layer are inclined with respect to a direction in which the first electrode and the second electrode face each other;
A method of manufacturing a thermoelectric device element, wherein power is taken out through the first electrode and the second electrode by applying a temperature difference in a direction perpendicular to the opposing direction,
The manufacturing method has the following steps:
A laminated structure forming step for obtaining a laminated structure in which YbAl 3 layers and metal layers are alternately laminated;
A laminate cutout step of obtaining the laminate by cutting out the laminate structure on a surface inclined with respect to the lamination direction of the laminate structure;
An electrode forming step of forming the first electrode and the second electrode on the laminate;
第1電極と、
前記第1電極に対向する第2電極と、
前記第1電極および前記第2電極との間に挟まれ、かつ前記第1電極および前記第2電極のいずれにも電気的に接続された積層体と
を具備し、
前記積層体は、YbAl3層と金属層とが交互に積層されてなり、
前記YbAl3層および前記金属層が、前記第1電極と前記第2電極とが対向する方向に対して傾斜している熱発電デバイス素子から、前記第1電極および前記第2電極をと介して電力を取り出す発電方法であって、
前記発電方法は以下の工程を包含する:
前記対向する方向に対して垂直方向に温度差を印加する、温度差印加工程。
A first electrode;
A second electrode facing the first electrode;
A laminated body sandwiched between the first electrode and the second electrode and electrically connected to both the first electrode and the second electrode;
The laminate is formed by alternately laminating YbAl 3 layers and metal layers,
From the thermoelectric device element in which the YbAl 3 layer and the metal layer are inclined with respect to the direction in which the first electrode and the second electrode face each other, through the first electrode and the second electrode A power generation method for extracting power,
The power generation method includes the following steps:
Applying a temperature difference in a direction perpendicular to the opposing direction;
前記YbAl3層および前記金属層が、前記第1電極と前記第2電極とが対 向する方向に対して角度θで傾斜しており、
前記角度θが20°以上60°以下である、請求項11に記載の発電方法。
The YbAl 3 layer and the metal layer are inclined at an angle θ with respect to a direction in which the first electrode and the second electrode face each other;
The power generation method according to claim 11, wherein the angle θ is 20 ° or more and 60 ° or less.
前記角度θが30°以上50°以下である、
請求項12に記載の発電方法。
The angle θ is 30 ° or more and 50 ° or less,
The power generation method according to claim 12.
前記金属層がCu、Ag、またはAuからなる、
請求項11に記載の発電方法。
The metal layer is made of Cu, Ag, or Au;
The power generation method according to claim 11.
前記金属層がCuまたはAgからなる、
請求項13に記載の発電方法。
The metal layer is made of Cu or Ag;
The power generation method according to claim 13.
前記金属層の厚み:前記YbAl3層の厚みの比が97:3から50:50までの範囲内にある、
請求項11に記載の発電方法。
The ratio of the thickness of the metal layer to the thickness of the YbAl 3 layer is in the range of 97: 3 to 50:50.
The power generation method according to claim 11.
前記金属層の厚み:前記YbAl3層の厚みの比が95:5から90:10までの範囲内にある、
請求項16に記載の発電方法。
The ratio of the thickness of the metal layer to the thickness of the YbAl 3 layer is in the range of 95: 5 to 90:10.
The power generation method according to claim 16.
前記金属層が、Cu、Ag、またはAuからなり、
前記金属層の厚み:前記YbAl3層の厚みの比が97:3から50:50までの範囲内にある、
請求項12に記載の発電方法。
The metal layer is made of Cu, Ag, or Au,
The ratio of the thickness of the metal layer to the thickness of the YbAl 3 layer is in the range of 97: 3 to 50:50.
The power generation method according to claim 12.
前記金属層が、CuまたはAgからなり、
前記金属層の厚み:前記YbAl3層の厚みの比が95:5から90:10までの範囲内にある、請求項13に記載の発電方法。
The metal layer is made of Cu or Ag;
14. The power generation method according to claim 13, wherein a ratio of the thickness of the metal layer to the thickness of the YbAl 3 layer is in a range of 95: 5 to 90:10.
支持板と、
前記支持板上に設けられた複数個の熱発電デバイス素子と、
を具備し、
前記熱発電デバイス素子は、請求項1に記載の熱発電デバイス素子であって、
隣接する2つの前記熱発電デバイス素子の一端を電気的に接続する各接続電極によって前記複数個の熱発電デバイス素子が電気的に直列に接続されており、
電気的に直列に接続されている前記複数個の熱発電デバイス素子の2つの終端には、それぞれ取り出し電極が接続されており、
前記支持板の法線方向に沿って温度差が印加されることによって、前記取り出し電極を介して電力が取り出される、熱発電デバイス。
A support plate;
A plurality of thermoelectric device elements provided on the support plate;
Comprising
The thermoelectric device element is the thermoelectric device element according to claim 1,
The plurality of thermoelectric generation device elements are electrically connected in series by each connection electrode that electrically connects one end of two adjacent thermoelectric generation device elements,
An extraction electrode is connected to each of the two ends of the plurality of thermoelectric device elements that are electrically connected in series,
A thermoelectric generation device in which electric power is extracted through the extraction electrode when a temperature difference is applied along a normal direction of the support plate.
支持板と、
前記支持板上に設けられた複数個の熱発電デバイス素子と
を具備し、
前記熱発電デバイス素子は、請求項1に記載の熱発電デバイス素子であって、
各熱発電デバイス素子の両端をそれぞれ電気的に接続する2つの取り出し電極によって前記複数個の熱発電デバイス素子が電気的に並列に接続されており、
前記支持板の法線方向に沿って温度差が印加されることによって、前記取り出し電極を介して電力が取り出される、熱発電デバイス。
A support plate;
A plurality of thermoelectric device elements provided on the support plate;
The thermoelectric device element is the thermoelectric device element according to claim 1,
The plurality of thermoelectric device elements are electrically connected in parallel by two extraction electrodes that electrically connect both ends of each thermoelectric device element,
A thermoelectric generation device in which electric power is extracted through the extraction electrode when a temperature difference is applied along a normal direction of the support plate.
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