JPH10144969A - Thermoelectric conversion element - Google Patents
Thermoelectric conversion elementInfo
- Publication number
- JPH10144969A JPH10144969A JP8313148A JP31314896A JPH10144969A JP H10144969 A JPH10144969 A JP H10144969A JP 8313148 A JP8313148 A JP 8313148A JP 31314896 A JP31314896 A JP 31314896A JP H10144969 A JPH10144969 A JP H10144969A
- Authority
- JP
- Japan
- Prior art keywords
- type semiconductor
- thermoelectric conversion
- conversion element
- crystal
- junction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】この発明は、ダイヤモンド型
結晶構造を有するＳｉ、Ｇｅあるいはその合金系に添加
元素を添加した単結晶Ｐ型半導体とＮ型半導体をＰＮ接
合した熱電変換素子の改良に係り、単結晶Ｐ型半導体と
Ｎ型半導体の各々の結晶の＜１１１＞方向の結晶方位に
温度勾配を与えるような構造にして、発電能力（変換効
率）を向上させた熱電変換素子に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an improvement in a thermoelectric conversion element in which a single crystal P-type semiconductor and an N-type semiconductor in which an additive element is added to Si, Ge or an alloy thereof having a diamond-type crystal structure are PN-joined. The present invention relates to a thermoelectric conversion element having a structure that gives a temperature gradient to the crystal orientation in the <111> direction of each of a single crystal P-type semiconductor and an N-type semiconductor to improve power generation capacity (conversion efficiency).
【０００２】[0002]
【従来の技術】熱電変換素子は、最近の産業界において
要求の高い熱エネルギーの有効活用の観点から実用化が
期待されているデバイスであり、例えば、排熱を利用し
電気エネルギーに変換するシステムや、屋外で簡単に電
気を得るための小型携帯用発電装置、ガス機器の炎セン
サー等、非常に広範囲の用途が検討されている。2. Description of the Related Art Thermoelectric conversion elements are devices that are expected to be put to practical use from the viewpoint of effective use of thermal energy, which is required in recent industries, and for example, a system that converts waste heat into electric energy. Also, a very wide range of applications such as a small portable power generator for easily obtaining electricity outdoors and a flame sensor for gas appliances are being studied.
【０００３】しかし、いままでに知られている熱電変換
素子は、一般に熱電変換素子の変換効率が低く、かつ使
用温度範囲が非常に狭いことや製造方法が煩雑でありコ
ストが高い等の理由から汎用されるには至っていない。However, the thermoelectric conversion elements known so far generally have a low conversion efficiency of the thermoelectric conversion element, a very narrow operating temperature range, a complicated manufacturing method and a high cost. It has not been widely used.
【０００４】現在変換効率を出来る限り上げるために、
半金属（Ａｓ，Ｓｂ，Ｂｉ，Ｃ）やカルコゲン元素
（Ｓ，Ｓｅ，Ｔｅ）をＳｉ、Ｇｅの半導体あるいは遷移
金属（Ｆｅ，Ｃｏ，Ｍｎ等）に添加した化合物を中心に
研究されているが、これらの化合物は電気的に半導体的
性質を示すために結晶方位によってゼーベック効果が一
般に大きく変化する。At present, in order to increase the conversion efficiency as much as possible,
Research has been focused on compounds in which semimetals (As, Sb, Bi, C) and chalcogen elements (S, Se, Te) are added to semiconductors of Si and Ge or transition metals (Fe, Co, Mn, etc.). Since these compounds show electrical semiconducting properties, the Seebeck effect generally largely varies depending on the crystal orientation.
【０００５】しかしながら今まで研究されてきた熱電変
換素子用の材料はほとんど多結晶体であり、特にゼーベ
ック係数の高い特定の結晶方位を選択することができな
いために、その変換効率にも自ずと限界があり、特に高
い熱電変換効率を実現するのは困難な状況である。However, most of the materials for thermoelectric conversion elements which have been studied so far are polycrystals. In particular, since a specific crystal orientation having a high Seebeck coefficient cannot be selected, the conversion efficiency is naturally limited. In particular, it is difficult to achieve particularly high thermoelectric conversion efficiency.
【０００６】また、一般にＳｉやＧｅの単結晶をＰ型半
導体あるいはＮ型半導体にするために、遷移金属元素、
アルカリ元素、第３族あるいは第５族元素等の添加元素
を添加して単結晶を育成することも可能であり、現在で
は添加元素によっては２原子％位まで添加が可能であ
る。さらに添加元素と添加量によって不純物エネルギー
準位を変えることができるために、熱電変換素子の使用
温度帯域を変化させることも可能である。In general, in order to convert a single crystal of Si or Ge into a P-type semiconductor or an N-type semiconductor, a transition metal element,
It is also possible to grow a single crystal by adding an additional element such as an alkali element, a Group 3 or Group 5 element, and at present it is possible to add up to about 2 atomic% depending on the additive element. Further, since the impurity energy level can be changed depending on the added element and the added amount, it is also possible to change the operating temperature band of the thermoelectric conversion element.
【０００７】[0007]
【発明が解決しようとする課題】熱電変換素子の熱起電
力は、原理的には熱電材料の一端を高温に熱し、他端を
低温にした時の温度差によって決まる。このような熱電
変換素子材料の研究は、主に半導体及び半導体特性を示
す金属間化合物を中心に行われてきた。その理由は、金
属や半金属に比べて熱伝導率が低く加えられることと、
各種添加物を添加することによりドナーレベルあるいは
アクセプターレベルで比較的高いエネルギー状態密度が
得られやすいので高いゼーベック効果が得られる利点が
あるためである。The thermoelectromotive force of a thermoelectric conversion element is determined in principle by a temperature difference when one end of a thermoelectric material is heated to a high temperature and the other end is cooled to a low temperature. Research on such thermoelectric conversion element materials has been mainly performed on semiconductors and intermetallic compounds exhibiting semiconductor characteristics. The reason is that the thermal conductivity is lower than that of metals and metalloids,
This is because a relatively high energy state density can be easily obtained at the donor level or the acceptor level by adding various additives, so that there is an advantage that a high Seebeck effect can be obtained.
【０００８】しかしながら前述したように、半導体のゼ
ーベック係数は一般に結晶方位によって大きく変化し、
特に結合力の弱い方位ではゼーベック係数は大きくな
り、また逆に強い結合力を示す結晶方位ではゼーベック
係数は小さくなる傾向を示す。これは結合力の弱い方位
では不純物エネルギー準位でのエネルギー状態密度が高
いことによる。However, as described above, the Seebeck coefficient of a semiconductor generally varies greatly depending on the crystal orientation.
In particular, the Seebeck coefficient tends to increase in an orientation having a weak binding force, and conversely tends to decrease in a crystal orientation exhibiting a strong binding force. This is because the energy state density at the impurity energy level is high in the direction where the bonding force is weak.
【０００９】言い換えれば、結晶のヘキカイ面（最密原
子面）に垂直方向（結合力の弱い方向）でゼーベック係
数が大きくなるということである。これはＳｉ単結晶で
は＜１１１＞方向の結晶方位でゼーベック係数が高くな
るということである。しかしながら半導体的特性を示す
金属間化合物の従来研究は殆ど多結晶体であるために、
ゼーベック係数の高い結晶方位の選択は困難であった。In other words, the Seebeck coefficient increases in the direction perpendicular to the cleavage plane (closest atomic plane) of the crystal (in the direction in which the bonding force is weak). This means that the Seebeck coefficient increases in the crystal orientation in the <111> direction in the Si single crystal. However, conventional research on intermetallic compounds exhibiting semiconducting properties is mostly polycrystalline,
It was difficult to select a crystal orientation having a high Seebeck coefficient.
【００１０】この発明は、従来の多結晶半導体とは異な
って、単結晶Ｐ型半導体とＮ型半導体とをＰＮ接合した
熱電変換素子において、特に高い熱起電力を発生させる
ことが可能な構成からなる熱電変換素子の提供を目的と
している。According to the present invention, unlike a conventional polycrystalline semiconductor, a thermoelectric conversion element having a PN junction of a single crystal P-type semiconductor and an N-type semiconductor can generate a particularly high thermoelectromotive force. The purpose of the present invention is to provide a thermoelectric conversion element.
【００１１】[0011]
【課題を解決するための手段】発明者らは、ダイヤモン
ド型結晶構造を有するＰ型半導体とＮ型半導体のＰＮ接
合による熱起電力特性をできるかぎり向上させるため
に、ダイヤモンド型結晶構造を有するＳｉ、Ｇｅあるい
はその合金系を中心に、その単結晶Ｐ型半導体とＮ型半
導体の結晶方位別に熱起電力特性を種々検討した結果、
単結晶の方位によって熱起電力特性が大きく変化するこ
と、またその時、単結晶Ｐ型半導体とＮ型半導体をＰＮ
接合する金属種によっても熱起電力特性が大きく変化す
ることを知見した。SUMMARY OF THE INVENTION The inventors of the present invention have proposed a Si-type crystal having a diamond-type crystal structure in order to improve as much as possible the thermoelectromotive force characteristics of a PN junction between a P-type semiconductor having a diamond-type crystal structure and an N-type semiconductor. As a result of various examinations of the thermoelectromotive force characteristics according to the crystal orientation of the single crystal P-type semiconductor and the N-type semiconductor, focusing on, Ge or its alloy system,
The thermo-electromotive force characteristic greatly changes depending on the orientation of the single crystal. At this time, the single crystal P-type semiconductor and the N-type semiconductor
It was found that the thermoelectromotive force characteristics also changed significantly depending on the type of metal to be joined.
【００１２】すなわち、発明者らは、ダイヤモンド型結
晶構造を有するＳｉ、Ｇｅの炭素族の外穀電子はＳ電子
２個とＰ電子２個からなり、ダイヤモンド型結晶構造の
四面体配位ではその結合はＳＰ3混成軌道のσ結合を形
成し、その波動関数は結晶の＜１１１＞方向に大きく伸
びており、大きな異方性を有するので、結晶の＜１１１
＞方向での結合に関与する電子のエネルギー状態密度は
非常に高くなっていることから、＜１１１＞方向での熱
起電力特性は非常に高くなることを知見した。さらに発
明者らは、単結晶Ｐ型半導体とＮ型半導体のＰＮ接合に
使用する金属を種々検討した結果、金や銀の貴金属が高
い熱起電力特性を示すことを知見し、この発明を完成し
た。In other words, the inventors have found that the outer electrons of the carbon group of Si and Ge having a diamond-type crystal structure consist of two S electrons and two P electrons. The bond forms a σ bond of SP 3 hybrid orbitals, and its wave function extends greatly in the <111> direction of the crystal and has a large anisotropy.
Since the energy state density of electrons involved in the binding in the> direction is very high, it has been found that the thermoelectromotive force characteristics in the <111> direction are very high. Furthermore, the present inventors have studied various metals used for the PN junction of a single-crystal P-type semiconductor and an N-type semiconductor, and have found that gold and silver noble metals exhibit high thermoelectric properties, and completed the present invention. did.
【００１３】この発明は、ダイヤモンド型結晶構造を有
するＳｉ、Ｇｅの炭素族のＰ型半導体とＮ型半導体をＰ
Ｎ接合した熱電変換素子において、各半導体の＜１１１
＞方向に温度勾配がかかるように組み上げ、さらに該一
対の半導体間を貴金属（Ａｕ，Ａｇ）のいずれか１種の
金属で接合させた熱電変換素子である。According to the present invention, a P-type semiconductor and an N-type semiconductor of a carbon group of Si and Ge having a diamond type crystal structure are
In the N-junction thermoelectric conversion element, <111
The thermoelectric conversion element is assembled in such a manner that a temperature gradient is applied in the direction, and the pair of semiconductors is joined with any one of noble metals (Au, Ag).
【００１４】[0014]
【発明の実施の形態】図１、図２はこの発明の熱電変換
素子の一実施例を示す斜視説明図である。まず、Ｓｉあ
るいはＧｅを主体とするＰ型半導体１、Ｎ型半導体３を
略Ｌ字型に加工して形成したＰＮ接合部を構成するため
の突起部端面２に、貴金属（Ａｕ，Ａｇ）のいずれか１
種の金属膜を形成する。金属膜の形成方法は当該端面に
蒸着やスパッタリング法で形成する他、後述の素子の圧
着組立時にＰ型半導体１とＮ型半導体３の突起部端面
２、４間に金属箔を介在させることもできる。この金属
膜あるいは金属箔の厚みは、１〜２０μｍが好ましい。1 and 2 are perspective explanatory views showing one embodiment of a thermoelectric conversion element of the present invention. First, a noble metal (Au, Ag) is formed on a projection end face 2 for forming a PN junction formed by processing a P-type semiconductor 1 and an N-type semiconductor 3 mainly composed of Si or Ge into a substantially L-shape. Any one
A seed metal film is formed. The metal film may be formed by vapor deposition or sputtering on the end face, or a metal foil may be interposed between the protruding end faces 2 and 4 of the P-type semiconductor 1 and the N-type semiconductor 3 at the time of crimping and assembling the element described below. it can. The thickness of the metal film or the metal foil is preferably 1 to 20 μm.
【００１５】この発明の熱電変換素子に用いる材料は、
Ｓｉ、ＳｉＧｅ合金、ＦｅＳｉ2、Ｇｄ2Ｓｅ3等の単結
晶体やＦｅ，Ｃｏ，Ｍｎ等の遷移金属が主体として用い
られる。熱電変換効率を上げるために、半金属（Ａｓ，
Ｓｂ，Ｂｉ，Ｃ）やカルコゲン元素（Ｓ，Ｓｅ，Ｔｅ）
をドーブすることが望ましい。また、ＳｉやＧｅの単結
晶をＰ型半導体あるいはＮ型半導体にするために遷移金
属元素、アルカリ元素、第３族あるいは第４族元素等の
添加元素を添加して単結晶を育成してもよい。Materials used for the thermoelectric conversion element of the present invention are as follows:
Single crystals such as Si, SiGe alloys, FeSi 2 and Gd 2 Se 3 and transition metals such as Fe, Co and Mn are mainly used. In order to increase thermoelectric conversion efficiency, semimetals (As,
Sb, Bi, C) and chalcogen elements (S, Se, Te)
It is desirable to do. Further, in order to convert a single crystal of Si or Ge into a P-type semiconductor or an N-type semiconductor, a single crystal may be grown by adding an additional element such as a transition metal element, an alkali element, or a Group 3 or Group 4 element. Good.
【００１６】ＰＮ接合部を構成するための金属膜とし
て、貴金属（Ａｕ，Ａｇ）を選定する理由としては、貴
金属は伝導電子としてそれぞれ５Ｓ、６Ｓ状態のＳ電子
のみを有するために高い電気伝導度を示し、半導体との
接合性に優れ、かつ酸化されにくいために接合部材とし
て使用すると、従来の銀ろうや遷移金属をベースにした
金属の接合に比べて高い熱電力が発生すること、また、
貴金属は化学的に安定であり大気中での加熱でも酸化さ
れにくいことから、貴金属と半導体との間の界面構造も
安定化して熱起電力と電流値が安定するためである。The reason for selecting a noble metal (Au, Ag) as a metal film for forming a PN junction is that noble metal has only 5S and 6S S electrons as conduction electrons, respectively, and thus has a high electric conductivity. Shows that, when used as a bonding member because it has excellent bondability with a semiconductor and is not easily oxidized, a higher thermal power is generated as compared with the conventional bonding of a metal based on silver solder or a transition metal, and
This is because the noble metal is chemically stable and hardly oxidized even when heated in the air, so that the interface structure between the noble metal and the semiconductor is also stabilized, so that the thermoelectromotive force and the current value are stabilized.
【００１７】ＰＮ接合する方法としては、Ｐ型半導体１
とＮ型半導体３の突起部端面２、４間に貴金属の金属膜
５または金属箔を介在させて、真空中もしくは不活性ガ
ス雰囲気中で、両半導体１，３をセラミックス製の挟持
治具で挟持し、圧力１００〜４００ｋｇ／ｃｍ2、温度
８００〜１２００℃、５〜２０分間の条件で圧着する方
法が採用できる。As a method of PN junction, a P-type semiconductor 1
A noble metal film 5 or a metal foil is interposed between the protruding end surfaces 2 and 4 of the N-type semiconductor 3 and the semiconductors 1 and 3 are held in a vacuum or an inert gas atmosphere by a holding jig made of ceramics. A method of clamping and pressing under a condition of pressure of 100 to 400 kg / cm 2 , temperature of 800 to 1200 ° C. for 5 to 20 minutes can be adopted.
【００１８】かかる圧着組立後に、この接合部を高温部
にするとともに、Ｐ型半導体、Ｎ型半導体１、３の他端
部を低温側端子として構成したＵ字型の熱電変換素子を
得ることができる。なお、Ｐ型半導体１とＮ型半導体３
の上端部には電気的接続を形成するリード６、７を設け
てある。また、ここで温度勾配の方向とは、Ｐ型半導体
１とＮ型半導体３の長手方向のことである。After this crimping assembly, it is possible to obtain a U-shaped thermoelectric conversion element in which this junction is made a high-temperature portion and the other ends of the P-type semiconductors and the N-type semiconductors 1, 3 are used as low-temperature terminals. it can. The P-type semiconductor 1 and the N-type semiconductor 3
Are provided with leads 6, 7 for forming electrical connection. Here, the direction of the temperature gradient is the longitudinal direction of the P-type semiconductor 1 and the N-type semiconductor 3.
【００１９】[0019]
実施例１ 図２に示す熱電変換素子を作製するため、珪素（Ｓｉ）
にＡｌを０．００３ｗｔ％ドープしたＰ型半導体の単結
晶と珪素（Ｓｉ）にＰを０．００３ｗｔ％ドープしたＮ
型半導体の単結晶を購入し、温度勾配が＜１１１＞にか
かるように切断加工した。この時のＰＮ接合を形成する
突起部端面の結晶方位は表１に示すとおりである。Example 1 In order to produce the thermoelectric conversion element shown in FIG. 2, silicon (Si) was used.
P-type semiconductor single crystal doped with 0.003 wt% of Al and N doped with 0.003 wt% of P in silicon (Si)
A single crystal of the type semiconductor was purchased and cut so that the temperature gradient was <111>. At this time, the crystal orientation of the end face of the projection forming the PN junction is as shown in Table 1.
【００２０】これら単結晶の突起部端面に真空蒸着でＡ
ｕ金属膜、Ａｇ金属膜を各１０μｍの厚みに成膜し、挟
持部材を用いて前記両半導体を挟持治具で挟持し、表１
に示す圧着条件にて接合した。得られた熱電変換素子の
高温部と低温部の温度差４００℃での熱電素子の熱起電
力を測定した。その結果を表１に示す。The end faces of the protruding portions of these single crystals are formed by vacuum evaporation.
u metal film and Ag metal film were formed to a thickness of 10 μm each, and the two semiconductors were sandwiched by a clamping jig using a clamping member.
The bonding was performed under the crimping conditions shown in FIG. The thermoelectromotive force of the thermoelectric element at a temperature difference of 400 ° C. between the high temperature part and the low temperature part of the obtained thermoelectric conversion element was measured. Table 1 shows the results.
【００２１】なお、熱電変換素子の低温側端子は、測定
用リード線とハンダ接合した。また熱電変換素子の熱起
電力の特性は、熱電素子のＰＮ接合部をヒーターで加熱
し、Ｕ字状の素子の両端部を水で冷却して、高温部と低
温部の温度差ΔＴによって生成される熱起電力をデジタ
ルマルチメーターで測定した。The low-temperature side terminal of the thermoelectric conversion element was soldered to a lead wire for measurement. The thermo-electromotive force characteristics of the thermoelectric conversion element are generated by heating the PN junction of the thermoelectric element with a heater, cooling both ends of the U-shaped element with water, and calculating the temperature difference ΔT between the high temperature part and the low temperature part. The measured thermoelectromotive force was measured with a digital multimeter.
【００２２】実施例２ 図２に示す熱電変換素子を作製するため、ゲルマニウム
（Ｇｅ）にＧａを０．００３ｗｔ％ドープしたＰ型半導
体の単結晶とゲルマニウム（Ｇｅ）にＡｓを０．００３
ｗｔ％ドープしたＮ型半導体の単結晶を購入し、温度勾
配が＜１１１＞にかかるように切断加工した。この時の
ＰＮ接合を形成する突起部端面の結晶方位は表１に示す
通りである。前記両半導体のＰＮ接合方法及び条件を表
１に示す。特に接合温度はＧｅの溶点９５９℃より低い
８５０℃に設定した。熱電素子の熱起電力の測定方法は
実施例１と同一条件であり、その測定結果を表１に示
す。Example 2 In order to fabricate the thermoelectric conversion element shown in FIG. 2, a P-type semiconductor single crystal in which germanium (Ge) is doped with 0.003 wt% of Ga and As is added in germanium (Ge) in an amount of 0.003%.
A single crystal of an N-type semiconductor doped with wt% was purchased and cut so as to have a temperature gradient of <111>. At this time, the crystal orientation of the end face of the projection forming the PN junction is as shown in Table 1. Table 1 shows PN junction methods and conditions of the two semiconductors. In particular, the joining temperature was set to 850 ° C., which is lower than the melting point of Ge, 959 ° C. The method of measuring the thermoelectromotive force of the thermoelectric element was the same as in Example 1, and the measurement results are shown in Table 1.
【００２３】実施例３ 図２に示す熱電変換素子を作製するため、Ｓｉ−ｌ０Ｇ
ｅの合金にＡｌを０．００３ｗｔ％ドープしたＰ型半導
体の単結晶と該合金にＰを０．００３ｗｔ％ドープした
Ｎ型半導体の単結晶を購入し、温度勾配が＜１１１＞に
かかるように切断加工した。切断加工後の両半導体のＰ
Ｎ接合方法及び条件は表１に示す。熱電素子の熱起電力
の測定方法は実施例１と同一条件であり、その測定結果
を表１に示す。Example 3 In order to produce the thermoelectric conversion element shown in FIG.
A single crystal of a P-type semiconductor doped with 0.003 wt% of Al in the alloy e and a single crystal of an N-type semiconductor doped with 0.003 wt% of P in the alloy are purchased so that the temperature gradient is <111>. It was cut. P of both semiconductors after cutting
Table 1 shows N bonding methods and conditions. The method of measuring the thermoelectromotive force of the thermoelectric element was the same as in Example 1, and the measurement results are shown in Table 1.
【００２４】比較例１〜３ 実施例１〜３と同一方法で熱電変換素子を作製する際、
従来の金属膜を真空蒸着で成膜して種々の比較例の熱電
変換素子を作製し、実施例と同様に測定した熱起電力を
表２に示す。また実施例１〜３の単結晶を真空アーク溶
解して多結晶体にした試料を切断加工し、実施例と同一
条件でＰＮ接合して熱電変換素子を作製し、実施例と同
様に測定した熱起電力を表２に示す。なお、表２の中で
適合、不適合の判定は温度差ΔＴ＝４００℃での熱起電
力値が６００ｍＶ以上かあるいは６００ｍＶ未満かで評
価した。Comparative Examples 1 to 3 When producing a thermoelectric conversion element in the same manner as in Examples 1 to 3,
Conventional metal films were formed by vacuum evaporation to produce thermoelectric conversion elements of various comparative examples, and the thermoelectromotive force measured in the same manner as in the examples is shown in Table 2. In addition, the single crystal of each of Examples 1 to 3 was cut into a polycrystal by vacuum arc melting to obtain a polycrystalline body, and a PN junction was formed under the same conditions as in the example to produce a thermoelectric conversion element, which was measured in the same manner as in the example. Table 2 shows the thermoelectromotive force. In Table 2, the determination of conformity or non-compliance was made based on whether the thermoelectromotive force at the temperature difference ΔT = 400 ° C. was 600 mV or more or less than 600 mV.
【００２５】さらに、さらに、実施例１〜３と同様の熱
電変換素子をＰＮ接合する際、従来から使用されている
材料を用いて実施例と同様に接合し、測定した熱起電力
を表３に示す。なお、表１〜表３の中の適合、不適合の
判定は温度差ΔＴ＝４００℃での熱起電力値が６００ｍ
Ｖ以上かあるいは６００ｍＶ未満かで評価した。Furthermore, when the PN junction of the same thermoelectric conversion element as in Examples 1 to 3 was performed, the thermoelectric power was measured using the conventionally used materials in the same manner as in Example. Shown in The determination of conformity or non-conformity in Tables 1 to 3 is based on the determination that the thermoelectromotive force at the temperature difference ΔT = 400 ° C. is 600 m.
The evaluation was made at V or higher or below 600 mV.
【００２６】[0026]
【表１】 [Table 1]
【００２７】[0027]
【表２】 [Table 2]
【００２８】[0028]
【表３】 [Table 3]
【００２９】表１、表２から明らかなように、従来のＳ
ｉ、Ｇｅあるいはその合金の多結晶体の熱電変換素子の
代わりに、各種添加元素を添加した単結晶Ｐ型半導体と
Ｎ型半導体の＜１１１＞方向の結晶方位に温度勾配を与
えるような構造にして、且つＰＮ接合金属として貴金属
（Ａｕ，Ａｇ）を使用することにより、発電能力（変換
効率）の高い熱電変換素子が得られることがわかった。
また、ＰＮ接合する単結晶の方位は、温度勾配の方向で
ある＜１１１＞方向に幾何学的に垂直な方向になるが、
特に方位によって大きな変化がないことがわかった。As is clear from Tables 1 and 2, the conventional S
Instead of a polycrystalline thermoelectric conversion element of i, Ge or an alloy thereof, a structure in which a temperature gradient is given to the crystal orientation in the <111> direction of a single crystal P-type semiconductor and an N-type semiconductor to which various additional elements are added. Further, it was found that a thermoelectric conversion element having high power generation capacity (conversion efficiency) can be obtained by using a noble metal (Au, Ag) as the PN junction metal.
Also, the orientation of the single crystal that forms the PN junction is a direction geometrically perpendicular to the <111> direction, which is the direction of the temperature gradient.
In particular, it was found that there was no significant change depending on the direction.
【００３０】[0030]
【発明の効果】この発明による熱電変換素子は、ダイヤ
モンド型結晶構造を有する単結晶Ｐ型半導体とＮ型半導
体の各々の結晶の＜１１１＞方向の結晶方位に温度勾配
を与えるように、その一端側でＰＮ接合し、該ＰＮ接合
部を化学的に安定であり大気中での加熱でも酸化され難
い貴金属（Ａｕ，Ａｇ）からなる金属膜を介在させるこ
とにより、熱起電力特性を向上させることが可能であ
る。According to the thermoelectric conversion element of the present invention, one end of a single crystal P-type semiconductor and a N-type semiconductor having a diamond-type crystal structure is provided so as to give a temperature gradient to the crystal orientation in the <111> direction of each crystal. PN junction on the side and improving the thermoelectromotive force characteristics by interposing a metal film made of a noble metal (Au, Ag) that is chemically stable and hardly oxidized even when heated in the air. Is possible.
【図１】この発明による熱電変換素子の半導体を示す傾
視説明図である。FIG. 1 is a perspective explanatory view showing a semiconductor of a thermoelectric conversion element according to the present invention.
【図２】この発明による熱電変換素子を示す傾視説明図
である。FIG. 2 is a perspective explanatory view showing a thermoelectric conversion element according to the present invention.
１ Ｐ型半導体 ２，４ 突起部端面 ３ Ｎ型半導体 ５ 金属膜 ６，７ リード DESCRIPTION OF SYMBOLS 1 P-type semiconductor 2, 4 Protrusion end surface 3 N-type semiconductor 5 Metal film 6, 7 Lead
Claims (2)
Ｐ型半導体とＮ型半導体の各々の結晶の＜１１１＞方向
の結晶方位に温度勾配を与えるように、その一端側でＰ
Ｎ接合して該接合部を高温側として熱起電力を発生させ
る熱電変換素子。1. One end of a single-crystal P-type semiconductor and a N-type semiconductor having a diamond-type crystal structure at one end thereof so as to give a temperature gradient to the crystal orientation in the <111> direction.
A thermoelectric conversion element in which N junction is performed to generate a thermoelectromotive force with the junction being on the high temperature side.
の半導体間のＰＮ接合を貴金属（Ａｇ，Ａｕ）のいずれ
か１種の金属で接合させたことを特徴とする熱電変換素
子。2. The thermoelectric conversion element according to claim 1, wherein the PN junction between the pair of semiconductors of the thermoelectric conversion element is joined with any one of noble metals (Ag, Au).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8313148A JPH10144969A (en) | 1996-11-08 | 1996-11-08 | Thermoelectric conversion element |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8313148A JPH10144969A (en) | 1996-11-08 | 1996-11-08 | Thermoelectric conversion element |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH10144969A true JPH10144969A (en) | 1998-05-29 |
Family
ID=18037691
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8313148A Pending JPH10144969A (en) | 1996-11-08 | 1996-11-08 | Thermoelectric conversion element |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH10144969A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002021608A1 (en) * | 2000-09-04 | 2002-03-14 | Shin-Etsu Handotai Co., Ltd. | Thermoelement |
| AT410492B (en) * | 2000-05-02 | 2003-05-26 | Span Gerhard Dipl Ing Dr | THERMOELECTRIC ELEMENT WITH AT LEAST ONE N LAYER AND AT LEAST ONE P LAYER |
-
1996
- 1996-11-08 JP JP8313148A patent/JPH10144969A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AT410492B (en) * | 2000-05-02 | 2003-05-26 | Span Gerhard Dipl Ing Dr | THERMOELECTRIC ELEMENT WITH AT LEAST ONE N LAYER AND AT LEAST ONE P LAYER |
| US6762484B2 (en) | 2000-05-02 | 2004-07-13 | Gerhard Span | Thermoelectric element |
| WO2002021608A1 (en) * | 2000-09-04 | 2002-03-14 | Shin-Etsu Handotai Co., Ltd. | Thermoelement |
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