JP2016100374A - Power generating element - Google Patents

Power generating element Download PDF

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JP2016100374A
JP2016100374A JP2014234066A JP2014234066A JP2016100374A JP 2016100374 A JP2016100374 A JP 2016100374A JP 2014234066 A JP2014234066 A JP 2014234066A JP 2014234066 A JP2014234066 A JP 2014234066A JP 2016100374 A JP2016100374 A JP 2016100374A
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type semiconductor
poly
semiconductor layer
power generating
generating element
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伸 宮澤
Shin Miyazawa
伸 宮澤
浩紀 西村
Hironori Nishimura
浩紀 西村
泰 村上
Yasushi Murakami
泰 村上
隆氏 山崎
Takashi Yamazaki
隆氏 山崎
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NTS KK
Shinshu University NUC
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NTS KK
Shinshu University NUC
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Abstract

PROBLEM TO BE SOLVED: To provide a novel power generating element different from a conventional power generating element.SOLUTION: A power generating element 10 has a structural form in which a positive electrode 1, a p-type semiconductor layer 2, a ferroelectric layer 3, an n-type semiconductor layer 4 and a negative electrode 5 are arranged in this order. Alternatively, in order to increase a contact interface, a heterojunction structure in which the p-type semiconductor layer 2, the ferroelectric layer 3 and the n-type semiconductor layer 4 are not sequentially arranged but arranged in a mixed manner may be employed.SELECTED DRAWING: Figure 1

Description

本発明は、新しい発電素子に関する。   The present invention relates to a new power generation element.

発電素子の代表的なものとして、熱電発電素子、太陽光発電素子、温度差発電素子等が知られている。熱電発電素子は、熱と電力を変換する熱電素子の一種であり、２種類の異なる金属又は半導体を接合して、両端に温度差を生じさせると起電力が生じるゼーベック効果を利用するものである。この熱電発電素子は、温度差によって大きな電位差を得るためにｐ型半導体、ｎ型半導体を組み合わせて使用される。また、太陽光発電素子は、光起電力効果を利用し、光エネルギーを直接電力に変換するものであり、光電池とも呼ばれる。この太陽光発電素子は、一般的な一次電池や二次電池のように電力を蓄える蓄電池ではなく、光起電力効果によって光を電力に変換して出力する発電機であり、シリコン太陽電池、化合物半導体型太陽電池、色素増感型太陽電池等が知られている。また、温度差発電素子は、２種類の異なった半導体を用いた熱電変換素子（ペルチェ素子）を使用して、熱起電力を発生させるものである。   As typical power generation elements, thermoelectric power generation elements, solar power generation elements, temperature difference power generation elements, and the like are known. A thermoelectric power generation element is a kind of thermoelectric element that converts heat and electric power, and utilizes the Seebeck effect in which an electromotive force is generated when two different metals or semiconductors are joined to generate a temperature difference at both ends. . This thermoelectric power generation element is used in combination with a p-type semiconductor and an n-type semiconductor in order to obtain a large potential difference due to a temperature difference. Moreover, a photovoltaic power generation element uses a photovoltaic effect and converts light energy directly into electric power, and is also called a photovoltaic cell. This solar power generation element is not a storage battery that stores electric power like a general primary battery or secondary battery, but a generator that converts light into electric power by the photovoltaic effect and outputs it. Semiconductor type solar cells, dye-sensitized type solar cells and the like are known. The temperature difference power generation element generates thermoelectromotive force using a thermoelectric conversion element (Peltier element) using two different types of semiconductors.

なお、上記の各発電素子についての先行技術文献は枚挙にいとまがないが、後述する本発明に近い先行技術文献は存在しなかった。   In addition, although the prior art literature about each said electric power generation element is enumerated, the prior art literature close | similar to this invention mentioned later did not exist.

本発明は、上記した従来の発電素子とは異なる新しい発電素子を提供することを目的とする。   An object of the present invention is to provide a new power generation element different from the conventional power generation element described above.

本発明に係る発電素子は、正極と、ｐ型半導体層と、強誘電体層と、ｎ型半導体層と、負極とがその順で配置された構造形態を有することを特徴とする。   The power generating element according to the present invention has a structure in which a positive electrode, a p-type semiconductor layer, a ferroelectric layer, an n-type semiconductor layer, and a negative electrode are arranged in this order.

本発明に係る発電素子において、前記ｐ型半導体層が、ポリ（３，４−エチレンジオキシチオフェン）−ポリ（スチレンスルホン酸）、ポリ（３，４−エチレンジオキシチオフェン）−ポリ（ビニルスルホン酸）、ポリアニリン、ポリピロール、ポリチオフェン、ポリ（ｐ−フェニレン）ポリ（ｐ−フェニレン）ポリ（ｐ−フェニレン）、ポリフルオレン、ポリ（ｐ−ポリ（ｐ−フェニレンビニレン）、ポリチエニレンビニレン、グラフェン、ＣｕＡｌＯ２、ＣｕＧａＯ２、ＬｉＮｉＯ２から選ばれるｐ型半導性高分子であることが好ましいが、ホール伝導が観測されれば、列記したｐ型半導体材料に限定されない。 In the power generation element according to the present invention, the p-type semiconductor layer may be poly (3,4-ethylenedioxythiophene) -poly (styrenesulfonic acid), poly (3,4-ethylenedioxythiophene) -poly (vinylsulfone). Acid), polyaniline, polypyrrole, polythiophene, poly (p-phenylene) poly (p-phenylene) poly (p-phenylene), polyfluorene, poly (p-poly (p-phenylene vinylene), polythienylene vinylene, graphene, A p-type semiconducting polymer selected from CuAlO 2 , CuGaO 2 , and LiNiO 2 is preferable. However, as long as hole conduction is observed, the materials are not limited to the listed p-type semiconductor materials.

本発明に係る発電素子において、前記強誘電体層が、チタン酸バリウム、チタン酸ジルコン酸鉛、チタン酸鉛、ジルコン酸鉛、チタン酸ビスマスランタン、チタン酸カドミウム、ニオブ酸リチウム、タンタル酸リチウム、ビスマスフェライト、及びリチウムドープ酸化亜鉛から選ばれるいずれかの粒子を含むことが好ましいが、強誘電性が観測されれば、列記した強誘電性材料に限定されない。   In the power generating element according to the present invention, the ferroelectric layer is composed of barium titanate, lead zirconate titanate, lead titanate, lead zirconate, bismuth lanthanum titanate, cadmium titanate, lithium niobate, lithium tantalate, It is preferable to include any particle selected from bismuth ferrite and lithium-doped zinc oxide. However, if ferroelectricity is observed, the material is not limited to the listed ferroelectric materials.

本発明に係る発電素子において、前記ｎ型半導体層が、酸化スズ、アンチモンドープ酸化スズ、フッ素ドープ酸化スズ、ガリウムドープ酸化亜鉛、アルミドープ酸化亜鉛、ニオブドープチタン酸ストロンチウム、及び酸化カルシウムドープ酸化ジルコニウムから選ばれるいずれかの粒子を含むことが好ましいが、電子伝導が観測されれば、列記したｎ型半導体材料に限定されない。   In the power generating element according to the present invention, the n-type semiconductor layer includes tin oxide, antimony-doped tin oxide, fluorine-doped tin oxide, gallium-doped zinc oxide, aluminum-doped zinc oxide, niobium-doped strontium titanate, and calcium oxide-doped zirconium oxide. However, it is not limited to the listed n-type semiconductor materials as long as electron conduction is observed.

本発明に係る発電素子において、前記正極と前記負極とが異種材料であるように構成できる。   In the power generating element according to the present invention, the positive electrode and the negative electrode can be made of different materials.

本発明に係る発電素子によれば、従来の発電素子とは異なる新しい発電素子を提供することができる。この発電素子は、高い電流を発生する発電現象を起こすことができ、特に恒温槽中で常温（例えば２５℃）から昇温することにより実現できる。   According to the power generation element according to the present invention, a new power generation element different from the conventional power generation element can be provided. This power generation element can cause a power generation phenomenon that generates a high current, and can be realized particularly by raising the temperature from room temperature (for example, 25 ° C.) in a thermostatic bath.

本発明に係る発電素子の一例を示す模式的な構成図である。It is a typical block diagram which shows an example of the electric power generating element which concerns on this invention. 本発明に係る発電素子の他の一例を示す模式的な構成図である。It is a typical block diagram which shows another example of the electric power generating element which concerns on this invention.

本発明に係る発電素子について、図面を参照しつつ説明する。以下に説明する発電素子は、本発明の実施例であり、本発明の要旨の範囲である限り以下の実施例に限定されない。   The power generation element according to the present invention will be described with reference to the drawings. The power generation element described below is an example of the present invention and is not limited to the following example as long as it is within the scope of the present invention.

［発電素子］
本発明に係る発電素子１０は、図１に示すように、正極１と、ｐ型半導体層２と、強誘電体層３と、ｎ型半導体層４と、負極５とがその順で配置された構造形態を有している。また、図２に示すように、ｐ型半導体層２と、強誘電体層３と、ｎ型半導体層４とは、接触界面を増やすために、順に並ばす、混合したヘテロジャンクション構造をとっていてもよい。こうした発電素子１０は、従来の発電素子とは異なる新しい発電素子であり、下記の実施例で示すように、高い電流を発生する発電現象を起こす。特に恒温槽中で常温（例えば２５℃）から昇温することにより実現できる。 [Power generation element]
As shown in FIG. 1, a power generating element 10 according to the present invention includes a positive electrode 1, a p-type semiconductor layer 2, a ferroelectric layer 3, an n-type semiconductor layer 4, and a negative electrode 5 arranged in that order. It has a different structural form. Also, as shown in FIG. 2, the p-type semiconductor layer 2, the ferroelectric layer 3, and the n-type semiconductor layer 4 have a mixed heterojunction structure that is arranged in order to increase the contact interface. May be. Such a power generation element 10 is a new power generation element different from the conventional power generation element, and causes a power generation phenomenon that generates a high current, as shown in the following embodiments. In particular, it can be realized by raising the temperature from room temperature (for example, 25 ° C.) in a thermostatic bath.

以下、本発明に係る発電素子１０の構成について説明する。   Hereinafter, the configuration of the power generation element 10 according to the present invention will be described.

（正極、負極）
正極１及び負極５は、導電性材料であり、正極１の仕事関数が負極５の仕事関数と同じか高い材料を用いる。正極１の仕事関数が負極５の仕事関数より高い方が望ましい。正極１としては、銅、銅合金、ＳＵＳ４３０等のステンレス鋼、錫めっき銅、銀、白金、金等を一例として挙げることができるが、これらの材料は、仕事関数を考慮して決定することができ、列記した前記正極材料に限定されない。負極５は、正極１とは異なる材料であればよく、例えば、アルミニウム又はアルミニウム合金、Ｍｇ−Ａｌ等のマグネシウム合金等の金属材料や、インジウム錫酸化物（ＩＴＯ）等の導電性酸化物材料等を挙げることができるが、これらの材料は、仕事関数を考慮して決定することができ、列記した前記負極材料に限定されない。 (Positive electrode, negative electrode)
The positive electrode 1 and the negative electrode 5 are conductive materials, and a material whose work function of the positive electrode 1 is the same as or higher than that of the negative electrode 5 is used. It is desirable that the work function of the positive electrode 1 is higher than that of the negative electrode 5. Examples of the positive electrode 1 include copper, copper alloy, stainless steel such as SUS430, tin-plated copper, silver, platinum, and gold. Examples of these materials may be determined in consideration of a work function. The positive electrode materials are not limited to the listed positive electrode materials. The negative electrode 5 may be a material different from that of the positive electrode 1. For example, a metal material such as aluminum or an aluminum alloy, a magnesium alloy such as Mg-Al, a conductive oxide material such as indium tin oxide (ITO), or the like. These materials can be determined in consideration of the work function, and are not limited to the negative electrode materials listed.

正極１及び負極５の形状も特に限定されず、発電素子１０の形状に応じた形状に加工することができる。例えば、発電素子１０が、平面配置型用の発電素子１０である場合には、正極１と負極５とを、ｐ型半導体層２、強誘電体層３及びｎ型半導体層４を挟んで対向配置して構成できる。なお、この平面配置型の発電素子１０は、正極１と負極５とを順次直列接続して直列配置型の発電素子複合体にしたり、正極１と負極５とを順次並列接続して並列配置型の発電素子複合体にしたりすることができる。また、発電素子１０を、乾電池型用の発電素子としてもよく、その場合は、中心を負極棒とし、周りを正極管として構成できる。   The shapes of the positive electrode 1 and the negative electrode 5 are not particularly limited, and can be processed into a shape corresponding to the shape of the power generation element 10. For example, when the power generation element 10 is a planar arrangement type power generation element 10, the positive electrode 1 and the negative electrode 5 are opposed to each other with the p-type semiconductor layer 2, the ferroelectric layer 3, and the n-type semiconductor layer 4 interposed therebetween. Can be arranged and configured. In addition, the planar arrangement type power generation element 10 includes a positive electrode 1 and a negative electrode 5 sequentially connected in series to form a series arrangement type power generation element composite, or a positive electrode 1 and a negative electrode 5 sequentially connected in parallel. Or a power generating element composite. The power generation element 10 may be a dry battery type power generation element, in which case the center may be a negative electrode rod and the periphery may be a positive electrode tube.

（ｐ型半導体層）
ｐ型半導体層２は、ポリ（３，４−エチレンジオキシチオフェン）−ポリ（スチレンスルホン酸）、ポリ（３，４−エチレンジオキシチオフェン）−ポリ（ビニルスルホン酸）、ポリアニリン、ポリピロール、ポリチオフェン、ポリ（ｐ−フェニレン）ポリ（ｐ−フェニレン）ポリ（ｐ−フェニレン）、ポリフルオレン、ポリ（ｐ−ポリ（ｐ−フェニレンビニレン）、ポリチエニレンビニレン、グラフェン、ＣｕＡｌＯ２、ＣｕＧａＯ２、ＬｉＮｉＯ２から選ばれるｐ型半導性高分子であることが好ましい。なお、ホール伝導が観測されれば、列記したｐ型半導体材料に限定されない。 (P-type semiconductor layer)
The p-type semiconductor layer 2 is composed of poly (3,4-ethylenedioxythiophene) -poly (styrenesulfonic acid), poly (3,4-ethylenedioxythiophene) -poly (vinylsulfonic acid), polyaniline, polypyrrole, polythiophene. , Poly (p-phenylene) poly (p-phenylene) poly (p-phenylene), polyfluorene, poly (p-poly (p-phenylene vinylene), polythienylene vinylene, graphene, CuAlO 2 , CuGaO 2 , LiNiO 2 The p-type semiconducting polymer is preferably selected from the following: If hole conduction is observed, it is not limited to the listed p-type semiconductor materials.

ｐ型半導体層２の厚さは、発電素子１０の作製方法によって異なり、特に限定されないが、例えば１０μｍ以上、１０００μｍ以下の範囲内であることが好ましい。なお、発電素子１０中でのｐ型半導体層２の境界は、そのｐ型半導体特性を奏する限り、図１に示すようにはっきり区分けされていてもよいし、図２に示すように、ｐ型半導体層２が強誘電体層３とｎ型半導体層４ともに、接触界面を増やすために、順に並ばす、混合したヘテロジャンクション構造をとっていてもよい。したがって、上記の厚さ範囲も、ｐ型半導体層２の作用を奏する範囲での厚さとして表すことができる。   The thickness of the p-type semiconductor layer 2 varies depending on the method of manufacturing the power generation element 10 and is not particularly limited, but is preferably in the range of 10 μm or more and 1000 μm or less, for example. Note that the boundary of the p-type semiconductor layer 2 in the power generation element 10 may be clearly divided as shown in FIG. 1 as long as the p-type semiconductor characteristics are exhibited, or as shown in FIG. The semiconductor layer 2 may have a mixed heterojunction structure in which both the ferroelectric layer 3 and the n-type semiconductor layer 4 are arranged in order to increase the contact interface. Therefore, the above thickness range can also be expressed as a thickness within a range where the p-type semiconductor layer 2 functions.

（強誘電体層）
強誘電体層３は、チタン酸バリウム、チタン酸ジルコン酸鉛、チタン酸鉛、ジルコン酸鉛、チタン酸ビスマスランタン、チタン酸カドミウム、ニオブ酸リチウム、タンタル酸リチウム、ビスマスフェライト、及びリチウムドープ酸化亜鉛から選ばれるいずれかの粒子を含むことが好ましい。なお、強誘電性が観測されれば、列記した強誘電性材料に限定されない。強誘電体層３は、前記材料の１種を単独で用いてもよいし、２種以上を用いてもよい。この強誘電体層３は、強誘電性を有する層であり、強誘電性を有するので発電をし、また、その強誘電体層３がさらにｎ型半導性を有する場合には電子（キャリア）の移動も容易であり、発電素子の構成要素として極めて望ましい。 (Ferroelectric layer)
Ferroelectric layer 3 is composed of barium titanate, lead zirconate titanate, lead titanate, lead zirconate, bismuth lanthanum titanate, cadmium titanate, lithium niobate, lithium tantalate, bismuth ferrite, and lithium-doped zinc oxide. It is preferable that any particle | grains chosen from these are included. If ferroelectricity is observed, the ferroelectric material is not limited to the listed ferroelectric materials. As the ferroelectric layer 3, one of the above materials may be used alone, or two or more thereof may be used. This ferroelectric layer 3 is a layer having ferroelectricity, and generates electric power because it has ferroelectricity. When the ferroelectric layer 3 further has n-type semiconductivity, electrons (carriers) are used. ) Is easy to move, and is extremely desirable as a component of the power generation element.

強誘電体粒子の形状や粒径は特に限定されないが、全体的な形状が球形状又は略球形状、楕円形状又は略楕円形状であればよく、その表面がなめらかでも凹凸であってもよい。強誘電体粒子の平均粒径は、入手の容易さや素子作製上の問題がない範囲で各種の大きさのものを選択することができるが、平均粒径の大きいものほど誘電率も高いので好ましく用いることができる。また、強誘電体粒子の平均粒径を所望の値に設定することにより、表面積をコントロールできるという利点がある。強誘電体粒子の平均粒径は、原料の段階では走査型電子顕微鏡（ＳＥＭ）によって測定することができ、強誘電体層３を構成した後も走査型電子顕微鏡（ＳＥＭ）によって測定することができる。   The shape and particle size of the ferroelectric particles are not particularly limited, but the overall shape may be a spherical shape, a substantially spherical shape, an elliptical shape, or a substantially elliptical shape, and the surface may be smooth or uneven. The average particle size of the ferroelectric particles can be selected from various sizes within a range where there is no problem in terms of availability and device fabrication, but the larger the average particle size, the higher the dielectric constant. Can be used. Further, there is an advantage that the surface area can be controlled by setting the average particle size of the ferroelectric particles to a desired value. The average particle diameter of the ferroelectric particles can be measured by a scanning electron microscope (SEM) at the raw material stage, and can be measured by a scanning electron microscope (SEM) even after the ferroelectric layer 3 is formed. it can.

強誘電体層３は、強誘電体粒子で構成されているが、本発明の効果を阻害しない範囲で、強誘電性を有する他の無機物を含んでいてもよい。また、本発明の効果を阻害しない範囲で、導電性やｎ型半導性を有する他の無機物を含んでいてもよい。   The ferroelectric layer 3 is composed of ferroelectric particles, but may contain other inorganic substances having ferroelectricity as long as the effects of the present invention are not impaired. In addition, other inorganic substances having conductivity and n-type semiconductivity may be included as long as the effects of the present invention are not impaired.

（ｎ型半導体層）
ｎ型半導体層４は、酸化スズ、アンチモンドープ酸化スズ、フッ素ドープ酸化スズ、ガリウムドープ酸化亜鉛、アルミドープ酸化亜鉛、ニオブドープチタン酸ストロンチウム、及び酸化カルシウムドープ酸化ジルコニウムから選ばれるいずれかの粒子を含むことが好ましい。なお、電子伝導が観測されれば、列記したｎ型半導体材料に限定されない。この粒子は、ｎ型半導体粒子であり、１種を単独で用いてもよいし、２種以上を用いてもよい。 (N-type semiconductor layer)
The n-type semiconductor layer 4 is made of any particle selected from tin oxide, antimony-doped tin oxide, fluorine-doped tin oxide, gallium-doped zinc oxide, aluminum-doped zinc oxide, niobium-doped strontium titanate, and calcium oxide-doped zirconium oxide. It is preferable to include. In addition, if electronic conduction is observed, it is not limited to the n-type semiconductor material listed. These particles are n-type semiconductor particles, and one kind may be used alone, or two or more kinds may be used.

ｎ型半導体粒子の粒子形状や粒径は特に限定されないが、全体的な形状が球形状又は略球形状、楕円形状又は略楕円形状であればよく、その表面がなめらかでも凹凸であってもよい。ｎ型半導体粒子の平均粒径は、入手の容易さや素子作製上の問題がない範囲で各種の大きさのものを選択することができるが、平均粒径の大きいものほど導電率が高いので好ましく用いることができる。また、ｎ型半導体粒子の平均粒径を所望の値に設定することにより、表面積をコントロールできるという利点がある。ｎ型半導体粒子の平均粒径は、原料の段階では走査型電子顕微鏡（ＳＥＭ）によって測定することができ、ｎ型半導体層４を構成した後も走査型電子顕微鏡（ＳＥＭ）によって測定することができる。   The particle shape and particle size of the n-type semiconductor particles are not particularly limited, but the overall shape may be a spherical shape, a substantially spherical shape, an elliptical shape, or a substantially elliptical shape, and the surface may be smooth or uneven. . The average particle size of the n-type semiconductor particles can be selected from various sizes within a range where there is no problem in terms of availability and device fabrication, but the larger the average particle size, the higher the conductivity, which is preferable. Can be used. Moreover, there is an advantage that the surface area can be controlled by setting the average particle size of the n-type semiconductor particles to a desired value. The average particle size of the n-type semiconductor particles can be measured by a scanning electron microscope (SEM) at the raw material stage, and can be measured by a scanning electron microscope (SEM) even after the n-type semiconductor layer 4 is formed. it can.

ｎ型半導体層４は、ｎ型半導体粒子で構成されているが、本発明の効果を阻害しない範囲で、ｎ型になり得る他の無機物を含んでいてもよい。   The n-type semiconductor layer 4 is composed of n-type semiconductor particles, but may contain other inorganic substances that can be n-type as long as the effects of the present invention are not impaired.

ｎ型半導体層４の抵抗は特に限定されないが、例えば２Ω以上、７Ω以下程度の範囲内が好ましい。ｎ型半導体層４をこうした範囲の抵抗にすることによって、内部インピーダンスを下げて電流を取り出しやすくするという利点がある。ｎ型半導体層４の抵抗は、ＬＣＲハイテスタによって測定することができる。ｎ型半導体層４の抵抗が２ｋΩ未満の場合、より具体的には例えば１ｋΩ未満や１００ｋΩ未満の場合は、そのｎ型半導体層４上に設けられる導電性のｐ型半導体層２がｎ型半導体層４中に浸入してショート状態になってしまい、発電素子として作動しないことがある。   The resistance of the n-type semiconductor layer 4 is not particularly limited, but is preferably in the range of, for example, about 2Ω or more and 7Ω or less. By making the resistance of the n-type semiconductor layer 4 in such a range, there is an advantage that the internal impedance is lowered and the current can be easily taken out. The resistance of the n-type semiconductor layer 4 can be measured by an LCR high tester. When the resistance of the n-type semiconductor layer 4 is less than 2 kΩ, more specifically, for example, when the resistance is less than 1 kΩ or less than 100 kΩ, the conductive p-type semiconductor layer 2 provided on the n-type semiconductor layer 4 is an n-type semiconductor. It may enter the layer 4 and become short-circuited, and may not operate as a power generation element.

（発電素子の作製方法）
発電素子１０は、上記構成を備えるものであれば、各種の方法で作製することができる。図１に示す発電素子１０は、正極１と、ｐ型半導体層２と、強誘電体層３と、ｎ型半導体層４と、負極５とがその順で配置された構造形態であり、図２に示す発電素子１０は、正極１と負極５とが、ｐ型半導体層２と強誘電体層３とｎ型半導体層４とが混合したヘテロジャンクション構造である。 (Method for producing power generation element)
The power generation element 10 can be manufactured by various methods as long as it has the above-described configuration. A power generation element 10 shown in FIG. 1 has a structure in which a positive electrode 1, a p-type semiconductor layer 2, a ferroelectric layer 3, an n-type semiconductor layer 4, and a negative electrode 5 are arranged in that order. The power generating element 10 shown in FIG. 2 has a heterojunction structure in which a positive electrode 1 and a negative electrode 5 are mixed with a p-type semiconductor layer 2, a ferroelectric layer 3, and an n-type semiconductor layer 4.

この発電素子１０の作製は特に限定されないが、正極１上に、ｎ型半導体層４、強誘電体層３、ｐ型半導体層２を順に形成する。ｐ型半導体層２は、ｐ型半導性高分子を例えば滴下又は塗布して形成することができる。強誘電体層３とｎ型半導体層４は、それぞれの粒子を例えば加圧成形して形成することができる。   Although the production of the power generation element 10 is not particularly limited, the n-type semiconductor layer 4, the ferroelectric layer 3, and the p-type semiconductor layer 2 are sequentially formed on the positive electrode 1. The p-type semiconductor layer 2 can be formed by dropping or coating a p-type semiconducting polymer, for example. The ferroelectric layer 3 and the n-type semiconductor layer 4 can be formed by, for example, pressure molding each particle.

こうして作製された発電素子部材は、平面的な直列構造又は並列構造になるように接続することができる。発電素子部材を直列接続して発電素子複合体を構成する場合、隣り合う発電素子部材の正極１と負極５とを、カシメ、圧接、ロウ付け等で接続して直列構造にすることができる。また、発電素子部材を並列接続して発電素子複合体を構成する場合、長く延びる電極に、発電素子部材の正極１と負極５をそれぞれ、カシメ、圧接、ロウ付け等で接続して並列構造にすることができる。   The power generating element members thus manufactured can be connected so as to have a planar series structure or a parallel structure. When a power generation element complex is configured by connecting power generation element members in series, the positive electrode 1 and the negative electrode 5 of adjacent power generation element members can be connected by caulking, pressure welding, brazing, or the like to form a series structure. Further, when a power generating element composite is configured by connecting power generating element members in parallel, the positive electrode 1 and the negative electrode 5 of the power generating element member are connected to the long extending electrode by caulking, pressure welding, brazing, etc., respectively, to form a parallel structure. can do.

このような発電素子複合体は、複数の発電素子部材を接続して１次元的（直列配置）又は二次元的（並列配置）に作製することができるが、厚さ方向に積層して三次元的な立体構造にすることもできる。   Such a power generation element composite can be produced in a one-dimensional (series arrangement) or two-dimensional (parallel arrangement) by connecting a plurality of power generation element members, but is laminated in the thickness direction and is three-dimensional. A three-dimensional structure can also be obtained.

なお、乾電池型用の発電素子としてもよく、その場合、底のある正極管の中に、ｎ型半導体粒子や強誘電体粒子の投入と、ｐ型半導性高分子材料の滴下又は塗布とを繰り返し、それらを層状に形成することができる。なお、負極棒は、ｎ型半導体層４と強誘電体層３とｐ型半導体層２との層状構造の形成前又は形成後に、正極管の中央に、その正極管に接触しないようにして挿入すればよい。   In addition, a power generation element for a dry cell type may be used, in which case, n-type semiconductor particles or ferroelectric particles are put into a bottomed cathode tube, and p-type semiconducting polymer material is dropped or applied. Can be repeated to form them in layers. The negative electrode rod is inserted into the center of the positive electrode tube before or after the formation of the layered structure of the n-type semiconductor layer 4, the ferroelectric layer 3, and the p-type semiconductor layer 2 so as not to contact the positive electrode tube. do it.

発電素子部材や発電素子複合体において、発電素子１０に水分が侵入するのを避けることが好ましい。水分の侵入防止手段としては、周囲を封止材で充填したり、全体を封止材で覆ったりすることが好ましい。こうした水分の侵入防止手段により、発電素子１０の発電電流値の低下を抑制することができる。   In the power generation element member or the power generation element complex, it is preferable to prevent moisture from entering the power generation element 10. As a means for preventing moisture from entering, it is preferable to fill the periphery with a sealing material or cover the whole with a sealing material. By such moisture intrusion prevention means, it is possible to suppress a decrease in the generated current value of the power generating element 10.

以上、本発明に係る発電素子によれば、従来の発電素子とは異なる新しい発電素子を提供することができた。この発電素子は、高い電流を発生する発電現象を起こすことができ、特に恒温槽中で常温（例えば２５℃）から昇温することにより実現できる。   As described above, according to the power generating element of the present invention, a new power generating element different from the conventional power generating element can be provided. This power generation element can cause a power generation phenomenon that generates a high current, and can be realized particularly by raising the temperature from room temperature (for example, 25 ° C.) in a thermostatic bath.

以下、実施例により本発明を更に詳しく説明する。   Hereinafter, the present invention will be described in more detail with reference to examples.

［実施例１］
図１に示す発電素子１０を作製した。先ず、厚さ０．２ｍｍ、縦１０ｍｍ、横１０ｍｍの平板状の銅部材を正極１として準備した。また、厚さ０．２ｍｍ、縦１０ｍｍ、横１０ｍｍの平板状のアルミニウム部材を負極５として準備した。次に、負極５上にニオブ酸リチウム粒子からなる厚さ２ｍｍのｎ型半導体層４を形成した。なお、このｎ型半導体層４は強誘電性も有している。次いで、その強誘電性を有するｎ型半導体層４の上から、液状のｐ型半導性高分子であるポリ（３，４−エチレンジオキシチオフェン）−ポリ（スチレンスルホナート））を滴下し、ｎ型半導体層４上にｐ型半導体層２を設けた。最後に、その上から負極５を載せて発電素子１０を作製した。得られた発電素子１０の電極間抵抗は２５ｋΩであった。 [Example 1]
A power generation element 10 shown in FIG. 1 was produced. First, a flat copper member having a thickness of 0.2 mm, a length of 10 mm, and a width of 10 mm was prepared as the positive electrode 1. A flat aluminum member having a thickness of 0.2 mm, a length of 10 mm, and a width of 10 mm was prepared as the negative electrode 5. Next, a 2 mm thick n-type semiconductor layer 4 made of lithium niobate particles was formed on the negative electrode 5. This n-type semiconductor layer 4 also has ferroelectricity. Next, poly (3,4-ethylenedioxythiophene) -poly (styrenesulfonate)), which is a liquid p-type semiconducting polymer, is dropped from above the n-type semiconductor layer 4 having ferroelectricity. The p-type semiconductor layer 2 is provided on the n-type semiconductor layer 4. Finally, the negative electrode 5 was placed thereon to produce the power generation element 10. The inter-electrode resistance of the obtained power generation element 10 was 25 kΩ.

（評価）
得られた発電素子を恒温糟に入れ、負荷抵抗１０Ωを接続し、Ｚ、Ｃｐ、Ｌ、ｔａｎδは 日置電機株式会社製のＬＣＲハイテスタ３５３２−５０を用いて測定し、電流と電圧は、ＦＬＵＫＥ社製のデジタルマルチメーター ８８０８Ａを用いて測定した。測定は、恒温層中の温度を変化させて行った。得られた結果を表１及び表２に示した。 (Evaluation)
The obtained power generation element was put in a thermostatic oven, a load resistance of 10Ω was connected, Z, Cp, L, and tan δ were measured using an LCR high tester 3532-50 manufactured by Hioki Electric Co., Ltd. It measured using the digital multimeter 8808A made from. The measurement was performed by changing the temperature in the constant temperature layer. The obtained results are shown in Tables 1 and 2.

Figure 2016100374
Figure 2016100374

Figure 2016100374
Figure 2016100374

１ 正極（正極板）
２ ｐ型半導体層
３ 強誘電体層
４ ｎ型半導体層
５ 負極（負極板）
１０ 発電素子 1 Positive electrode (positive electrode plate)
2 p-type semiconductor layer 3 ferroelectric layer 4 n-type semiconductor layer 5 negative electrode (negative electrode plate)
10 Power generation element

Claims (5)

正極と、ｐ型半導体層と、強誘電体層と、ｎ型半導体層と、負極とがその順で配置された構造形態を有することを特徴とする発電素子。   A power generating element having a structure in which a positive electrode, a p-type semiconductor layer, a ferroelectric layer, an n-type semiconductor layer, and a negative electrode are arranged in this order. 前記ｐ型半導体層が、ポリ（３，４−エチレンジオキシチオフェン）−ポリ（スチレンスルホン酸）、ポリ（３，４−エチレンジオキシチオフェン）−ポリ（ビニルスルホン酸）、ポリアニリン、ポリピロール、ポリチオフェン、ポリ（ｐ−フェニレン）ポリ（ｐ−フェニレン）ポリ（ｐ−フェニレン）、ポリフルオレン、ポリ（ｐ−ポリ（ｐ−フェニレンビニレン）、ポリチエニレンビニレン、グラフェン、ＣｕＡｌＯ２、ＣｕＧａＯ２、及びＬｉＮｉＯ２から選ばれるｐ型半導性高分子である、請求項１に記載の発電素子。 The p-type semiconductor layer is composed of poly (3,4-ethylenedioxythiophene) -poly (styrenesulfonic acid), poly (3,4-ethylenedioxythiophene) -poly (vinylsulfonic acid), polyaniline, polypyrrole, polythiophene. , poly (p- phenylene) poly (p- phenylene) poly (p- phenylene), polyfluorene, poly (p- poly (p- phenylenevinylene), polythienylenevinylene, graphene, CuAlO 2, CuGaO 2, and LiNiO The power generating element according to claim 1, wherein the power generating element is a p-type semiconducting polymer selected from 2 . 前記強誘電体層が、チタン酸バリウム、チタン酸ジルコン酸鉛、チタン酸鉛、ジルコン酸鉛、チタン酸ビスマスランタン、チタン酸カドミウム、ニオブ酸リチウム、タンタル酸リチウム、ビスマスフェライト、及びリチウムドープ酸化亜鉛から選ばれるいずれかの粒子を含む、請求項１又は２に記載の発電素子。   The ferroelectric layer is composed of barium titanate, lead zirconate titanate, lead titanate, lead zirconate, bismuth lanthanum titanate, cadmium titanate, lithium niobate, lithium tantalate, bismuth ferrite, and lithium-doped zinc oxide. The power generating element according to claim 1, comprising any particle selected from the group consisting of: 前記ｎ型半導体層が、酸化スズ、アンチモンドープ酸化スズ、フッ素ドープ酸化スズ、ガリウムドープ酸化亜鉛、アルミドープ酸化亜鉛、ニオブドープチタン酸ストロンチウム、及び酸化カルシウムドープ酸化ジルコニウムから選ばれるいずれかの粒子を含む、請求項１〜３のいずれか１項に記載の発電素子。   The n-type semiconductor layer may be any particle selected from tin oxide, antimony-doped tin oxide, fluorine-doped tin oxide, gallium-doped zinc oxide, aluminum-doped zinc oxide, niobium-doped strontium titanate, and calcium oxide-doped zirconium oxide. The power generating element according to any one of claims 1 to 3. 前記正極と前記負極とが異種材料である、請求項１〜４のいずれか１項に記載の発電素子。   The power generating element according to claim 1, wherein the positive electrode and the negative electrode are different materials.
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