JP2000332307A - Manufacture of thermoelectric material - Google Patents
Manufacture of thermoelectric materialInfo
- Publication number
- JP2000332307A JP2000332307A JP11137777A JP13777799A JP2000332307A JP 2000332307 A JP2000332307 A JP 2000332307A JP 11137777 A JP11137777 A JP 11137777A JP 13777799 A JP13777799 A JP 13777799A JP 2000332307 A JP2000332307 A JP 2000332307A
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- Prior art keywords
- powder
- thin film
- group
- element selected
- thermoelectric material
- Prior art date
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、熱電材料の製造方
法に関し、特に、低消費電力であることが求められるデ
バイス等に好適な熱電材料の製造方法に関する。The present invention relates to a method for producing a thermoelectric material, and more particularly to a method for producing a thermoelectric material suitable for devices requiring low power consumption.
【０００２】[0002]
【従来の技術】従来、熱電材料の製造方法としては、原
料粉末を所定の組成に秤量した後、溶解し、冷却条件を
適宜制御しながら凝固させることにより結晶性を制御す
る一方向凝固法が知られている。2. Description of the Related Art Conventionally, as a method for producing a thermoelectric material, a one-way solidification method in which a raw material powder is weighed to a predetermined composition, melted, and solidified while appropriately controlling cooling conditions to control crystallinity is known. Are known.
【０００３】また、熱電材料の製造方法としては、一方
向凝固法により作製された鋳塊を粉砕し、粉末とした
後、常圧でホットプレスにより固化成形する方法が知ら
れている。[0003] As a method for producing a thermoelectric material, a method is known in which an ingot produced by a unidirectional solidification method is pulverized into powder, and then solidified and formed by hot pressing at normal pressure.
【０００４】更に、熱電材料の製造方法としては、液体
急冷法により作製した液体急冷粉をホットプレスにより
形成する方法が知られている。Further, as a method for producing a thermoelectric material, a method is known in which a liquid quenched powder produced by a liquid quenching method is formed by hot pressing.
【０００５】一方、熱電材料の性能は、熱電材料の性能
指数をＺ、熱起電力をα、熱伝導率をκ、比抵抗をρと
するとき、下記数式１のように示される。この性能指数
Ｚの値が大きいほうが熱電材料の性能が優れている。[0005] On the other hand, the performance of a thermoelectric material is expressed by the following formula 1 when the figure of merit of the thermoelectric material is Z, the thermoelectromotive force is α, the thermal conductivity is κ, and the specific resistance is ρ. The larger the value of the figure of merit Z, the better the performance of the thermoelectric material.
【０００６】[0006]
【数１】Ｚ＝α2／（κ×ρ）## EQU1 ## Z = α 2 / (κ × ρ)
【０００７】[0007]
【発明が解決しようとする課題】しかし、上述の一方向
凝固法により製造された熱電材料は、熱伝導率κが大き
いため、性能指数Ｚが小さい。また、形成される結晶粒
が大きく結晶界面がへき開してしまうため、強度が低い
という問題点がある。However, the thermoelectric material manufactured by the above-described directional solidification method has a small thermal index κ and therefore a small figure of merit Z. Further, there is a problem that the strength is low because formed crystal grains are large and the crystal interface is cleaved.
【０００８】また、上述の一方向凝固法により作製され
た鋳塊を粉砕し、常圧でホットプレスにより製造された
熱電材料は、性能指数Ｚが小さいという問題点がある。A thermoelectric material produced by pulverizing an ingot produced by the above-described unidirectional solidification method and hot-pressing it at normal pressure has a problem that the figure of merit Z is small.
【０００９】更に、上述の液体急冷法により形成された
液体急冷粉をホットプレスにより製造された熱電材料は
性能指数Ｚは高いものの、比抵抗ρが大きいため、デバ
イスとしての用途が限定されてしまうという問題点があ
る。Further, the thermoelectric material produced by hot pressing the liquid quenched powder formed by the above-mentioned liquid quenching method has a high figure of merit Z, but has a large specific resistance ρ, so that its use as a device is limited. There is a problem.
【００１０】本発明はかかる問題点に鑑みてなされたも
のであって、低比抵抗かつ高い性能指数を有する低消費
電力が求められるデバイスに好適な熱電材料の製造方法
を提供することを目的とする。The present invention has been made in view of the above problems, and has as its object to provide a method for producing a thermoelectric material suitable for a device requiring low power consumption having a low specific resistance and a high figure of merit. I do.
【００１１】[0011]
【課題を解決するための手段】本発明に係る熱電材料の
製造方法は、Ｂｉ及びＳｂからなる群から選択された少
なくとも１種の元素と、Ｔｅ及びＳｅからなる群から選
択された少なくとも１種の元素とを含有する原料を液体
急冷法により薄膜又は粉末にする工程と、これにより得
られた薄膜又は粉末の結晶粒の配向性が乱れない条件で
ホットプレスにより固化成形する工程と、を有すること
を特徴とする。ここで、配向性が乱れない条件とは、固
化成形時の押圧方向に垂直な面（ｈｋｌ）のＸ線回折で
得られるピーク強度をＩhklとするとき、（１１０）面
と（０１５）面との強度比、（１１０）面と（１０１
０）面との強度比及び（１１０）面と（２０５）面との
強度比が夫々下記数式２乃至４で示される範囲内にある
ことをいう。According to the present invention, there is provided a method for producing a thermoelectric material, comprising: at least one element selected from the group consisting of Bi and Sb; and at least one element selected from the group consisting of Te and Se. And a step of solidifying and molding by hot pressing under conditions that the orientation of the crystal grains of the thin film or powder obtained thereby is not disturbed, and It is characterized by the following. Here, the condition under which the orientation is not disturbed means that the peak intensity obtained by X-ray diffraction of a plane (hkl) perpendicular to the pressing direction at the time of solidification molding is Ihkl, and the (110) plane and the (015) plane Intensity ratio between (110) plane and (101) plane.
It means that the intensity ratio with respect to the (0) plane and the intensity ratio between the (110) plane and the (205) plane are within the ranges represented by the following mathematical expressions 2 to 4, respectively.
【００１２】[0012]
【数２】Ｉ110／Ｉ015≧０．２## EQU2 ## I 110 / I 015 ≧ 0.2
【００１３】[0013]
【数３】Ｉ110／Ｉ1010≧０．５[Equation 3] I 110 / I 1010 ≧ 0.5
【００１４】[0014]
【数４】Ｉ110／Ｉ205≧０．５## EQU4 ## I 110 / I 205 ≧ 0.5
【００１５】本発明に係る他の熱電材料の製造方法は、
Ｂｉ及びＳｂからなる群から選択された少なくとも１種
の元素と、Ｔｅ及びＳｅからなる群から選択された少な
くとも１種の元素とを含有する原料を液体急冷法により
薄膜又は粉末にする工程と、これにより得られた薄膜又
は粉末を温度をＴ（℃）、圧力をＰ（ｋｇｆ／ｃｍ2）
とするとき、前記Ｔが２００≦Ｔ≦４００のとき、前記
Ｐは−（３９／２０）×Ｔ＋７９０≦Ｐ＜４００であ
り、前記Ｔが４００＜Ｔ≦６００のとき、前記Ｐは１０
≦Ｐ＜４００である条件でホットプレスにより固化成形
する工程と、を有することを特徴とする。Another method for producing a thermoelectric material according to the present invention is as follows.
Turning a raw material containing at least one element selected from the group consisting of Bi and Sb and at least one element selected from the group consisting of Te and Se into a thin film or powder by a liquid quenching method; The temperature of the obtained thin film or powder is T (° C.) and the pressure is P (kgf / cm 2 ).
When T is 200 ≦ T ≦ 400, P is − (39/20) × T + 790 ≦ P <400, and when T is 400 <T ≦ 600, P is 10
Solidifying and molding by hot pressing under the condition of ≦ P <400.
【００１６】この場合、前記原料は更にＩ、Ｃｌ、Ｈ
ｇ、Ｂｒ、Ａｇ及びＣｕからなる群から選択された少な
くとも１種の元素を含有させて、キャリア密度の制御が
可能である。In this case, the raw material further comprises I, Cl, H
The carrier density can be controlled by containing at least one element selected from the group consisting of g, Br, Ag, and Cu.
【００１７】本発明においては、前記ホットプレスによ
り固化成形する工程は、加熱時間をｔとするとき、前記
ｔは５乃至１５０分であることが好ましい。In the present invention, in the step of solidifying and molding by the hot press, when the heating time is t, it is preferable that the t is 5 to 150 minutes.
【００１８】また、前記Ｂｉ及びＳｂからなる群から選
択された少なくとも１種の元素と、Ｔｅ及びＳｅからな
る群から選択された少なくとも１種の元素とを含有する
原料を液体急冷法により薄膜又は粉末にする工程の後工
程として、前記薄膜又は粉末を粉砕する工程を有するこ
とが好ましい。Further, a raw material containing at least one element selected from the group consisting of Bi and Sb and at least one element selected from the group consisting of Te and Se is formed into a thin film or a thin film by a liquid quenching method. It is preferable to include a step of pulverizing the thin film or the powder as a step subsequent to the step of forming the powder.
【００１９】更に、前記Ｂｉ及びＳｂからなる群から選
択された少なくとも１種の元素と、Ｔｅ及びＳｅからな
る群から選択された少なくとも１種の元素とを含有する
原料を液体急冷法により薄膜又は粉末にする工程の後工
程として、前記薄膜又は粉末を水素雰囲気中で加熱する
工程を有することが好ましい。Further, a raw material containing at least one element selected from the group consisting of Bi and Sb and at least one element selected from the group consisting of Te and Se is formed into a thin film or a thin film by a liquid quenching method. It is preferable to include a step of heating the thin film or the powder in a hydrogen atmosphere as a step after the step of forming the powder.
【００２０】更にまた、前記薄膜又は粉末を粉砕する工
程の後工程として、水素雰囲気中で加熱する工程を有す
ることが望ましい。Further, it is preferable that the method further includes a step of heating in a hydrogen atmosphere as a step subsequent to the step of pulverizing the thin film or the powder.
【００２１】[0021]
【発明の実施の形態】以下、本発明の実施例に係る熱電
材料の製造方法について具体的に説明する。本願発明者
等はＢｉ及びＳｂからなる群から選択された少なくとも
１種の元素と、Ｔｅ及びＳｅからなる群から選択された
少なくとも１種の元素とを含有する原料を液体急冷法に
より薄膜又は粉末にし、これにより得られた薄膜又は粉
末の結晶粒の配向性が乱れない条件でホットプレスによ
り固化成形することにより、低比抵抗かつ高い性能指数
を有する熱電材料を製造することができることを見出し
た。図１は縦軸に圧力、横軸に温度をとり、本発明の実
施例に係る熱電材料のホットプレス条件の範囲を示すグ
ラフ図である。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, a method for manufacturing a thermoelectric material according to an embodiment of the present invention will be specifically described. The present inventors have prepared a thin film or powder of a raw material containing at least one element selected from the group consisting of Bi and Sb and at least one element selected from the group consisting of Te and Se by a liquid quenching method. It was found that a thermoelectric material having a low specific resistance and a high figure of merit can be produced by solidifying and molding by hot pressing under conditions where the orientation of the crystal grains of the thin film or powder obtained thereby is not disturbed. . FIG. 1 is a graph showing a range of hot pressing conditions of a thermoelectric material according to an embodiment of the present invention, with pressure on the vertical axis and temperature on the horizontal axis.
【００２２】以下、本発明に係るホットプレスの限定理
由について説明する。Hereinafter, the reasons for limiting the hot press according to the present invention will be described.
【００２３】ホットプレスの条件 温度をＴ（℃）、圧力をＰ（ｋｇｆ／ｃｍ2）とすると
き、ホットプレス条件は温度により下記数式５及び数式
６のように示すことができる。When the temperature of the hot press is T (° C.) and the pressure is P (kgf / cm 2 ), the hot press conditions can be represented by the following formulas 5 and 6 depending on the temperature.
【００２４】[0024]
【数５】−（３９／２０）×Ｔ＋７９０≦Ｐ＜４００ 但し、２００≦Ｔ≦４００-(39/20) × T + 790 ≦ P <400 where 200 ≦ T ≦ 400
【００２５】[0025]
【数６】５≦Ｐ＜４００ 但し、４００＜Ｔ≦６００5 ≦ P <400 where 400 <T ≦ 600
【００２６】図１に示すように、温度が２００乃至４０
０℃である領域Ｄでは、圧力が−（３９／２０）×Ｔ＋
７９０ｋｇｆ／ｃｍ2未満であると、圧力が低く焼結が
不十分となり、比抵抗が高くなり、性能指数が低下す
る。一方、圧力が４００ｋｇｆ／ｃｍ2以上であると、
結晶粒の配向性が乱れて比抵抗が高くなる。従って、温
度が２００乃至４００℃では、圧力は−（３９／２０）
×Ｔ＋７９０ｋｇｆ／ｃｍ2以上４００ｋｇｆ／ｃｍ2未
満であることが好ましい。As shown in FIG. 1, the temperature is 200 to 40.
In the region D where the temperature is 0 ° C., the pressure is − (39/20) × T +
If it is less than 790 kgf / cm 2 , the pressure is low and sintering becomes insufficient, the specific resistance increases, and the figure of merit decreases. On the other hand, when the pressure is 400 kgf / cm 2 or more,
The orientation of the crystal grains is disturbed, and the specific resistance increases. Therefore, when the temperature is 200 to 400 ° C., the pressure becomes − (39/20)
× T + 790 kgf / cm 2 or more and preferably less than 400 kgf / cm 2 .
【００２７】また、図１に示すように、温度が４００℃
を超え６００℃以下である領域Ｄでは、圧力が５ｋｇｆ
／ｃｍ2未満であると、圧力が低く焼結が不十分とな
り、比抵抗が高くなると共に性能指数が低下する。一
方、圧力が４００ｋｇｆ／ｃｍ2以上であると、高温、
高圧下の条件では、オーバーシンタリング（焼結過剰）
となり、成分元素の脱離が促進されるため、比抵抗は小
さくなるものの、性能指数が小さくなる。従って、温度
が４００℃を超え６００℃以下では、圧力は５ｋｇｆ／
ｃｍ2以上４００ｋｇｆ／ｃｍ2未満であることが好まし
い。Further, as shown in FIG.
In the region D in which the pressure is higher than 600 ° C. and the pressure is 5 kgf
If it is less than / cm 2 , the pressure will be low and sintering will be insufficient, the specific resistance will increase and the figure of merit will decrease. On the other hand, if the pressure is 400 kgf / cm 2 or more, high temperature,
Under high pressure conditions, oversintering (excessive sintering)
Since the desorption of the component elements is promoted, the specific resistance decreases, but the figure of merit decreases. Therefore, when the temperature exceeds 400 ° C. and is 600 ° C. or less, the pressure is 5 kgf /
It is preferably less than cm 2 or more 400 kgf / cm 2.
【００２８】本発明においては、圧力を２００乃至４０
０℃の温度で−（３９／２０）×Ｔ＋７９０ｋｇｆ／ｃ
ｍ2以上４００ｋｇｆ／ｃｍ2未満とし、また、圧力を４
００℃を超え６００℃以下の温度で１０ｋｇｆ／ｃｍ2
以上４００ｋｇｆ／ｃｍ2未満にしているので結晶粒の
配向性が乱れない。このため、固化形成時の押圧方向に
垂直な面のＸ線回折で得られるピーク強度は、Ｉ110／
Ｉ015≧０．２、Ｉ110／Ｉ1010≧０．５及びＩ110／Ｉ
205≧０．５である。しかし、従来の一般材料の固化形
成時の押圧方向に垂直な面のＸ線回折例ではＩ110／Ｉ
015＝０．１３、Ｉ11 0／Ｉ1010＝０．２３及びＩ110／
Ｉ205＝２．０である。In the present invention, the pressure is set to 200 to 40.
At a temperature of 0 ° C.,-(39/20) × T + 790 kgf / c
m 2 to less than 400 kgf / cm 2, and a pressure of 4
10 kgf / cm 2 at a temperature of more than 00 ° C and 600 ° C or less
Since it is less than 400 kgf / cm 2 , the orientation of crystal grains is not disturbed. For this reason, the peak intensity obtained by X-ray diffraction of a plane perpendicular to the pressing direction at the time of solidification is I 110 /
I 015 ≧ 0.2, I 110 / I 1010 ≧ 0.5 and I 110 / I
205 ≧ 0.5. However, in the conventional X-ray diffraction example of a plane perpendicular to the pressing direction at the time of solidification formation of a general material, I 110 / I
015 = 0.13, I 11 0 / I 1010 = 0.23 and I 110 /
I 205 = 2.0.
【００２９】なお、いずれの温度範囲においても、加熱
時間をｔとするとき、加熱時間ｔは５乃至１５０分であ
ることが好ましい。In any temperature range, when the heating time is t, the heating time t is preferably 5 to 150 minutes.
【００３０】また、液体急冷法により形成された薄膜又
は粉末を水素雰囲気中で熱処理してもよい。更に、液体
急冷法により形成された薄膜又は粉末を粉砕した後に水
素雰囲気中で熱処理することもできる。The thin film or powder formed by the liquid quenching method may be heat-treated in a hydrogen atmosphere. Further, a thin film or powder formed by the liquid quenching method may be pulverized and then heat-treated in a hydrogen atmosphere.
【００３１】[0031]
【実施例】以下、本実施例方法により製造された熱電材
料の実施例について、その比抵抗及び性能指数を比較例
と比較して具体的に説明する。EXAMPLES Examples of the thermoelectric material manufactured by the method of the present example will be specifically described by comparing the specific resistance and the figure of merit with those of a comparative example.
【００３２】先ず、下記表１に示す種々の組成を有する
熱電材料を下記表２に示すホットプレス条件により製造
し、これらの実施例及び比較例のサンプルについて、比
抵抗ρを測定すると共に、性能指数Ｚを算出した。これ
らの結果を表２に示す。First, thermoelectric materials having various compositions shown in Table 1 below were manufactured under the hot pressing conditions shown in Table 2 below. The samples of Examples and Comparative Examples were measured for the specific resistance ρ and the performance was measured. The index Z was calculated. Table 2 shows the results.
【００３３】[0033]
【表１】 [Table 1]
【００３４】[0034]
【表２】 [Table 2]
【００３５】上記表２に示すように、実施例No.１乃至
９は比抵抗が１．１０×１０-5Ω・ｍ以下と小さく、か
つ性能指数が４．０×１０-3／Ｋ以上と高かった。一
方、比較例No.１０乃至１２は比抵抗が小さく、かつ性
能指数が３．５×１０-3／Ｋ以上の高い値にはならなか
った。比較例No.１０は圧力が低いため、焼結が不十分
となり比抵抗が大きくなり、性能指数が小さくなった。As shown in the above Table 2, Examples Nos. 1 to 9 have a small specific resistance of 1.10 × 10 −5 Ω · m or less and a performance index of 4.0 × 10 −3 / K or more. And it was high. On the other hand, in Comparative Examples Nos. 10 to 12, the specific resistance was small and the figure of merit did not become a high value of 3.5 × 10 −3 / K or more. In Comparative Example No. 10, since the pressure was low, sintering was insufficient, the specific resistance increased, and the figure of merit decreased.
【００３６】比較例No.１１は圧力が高いため、結晶粒
の配向性が乱れ比抵抗が増大し、性能指数が小さくなっ
た。In Comparative Example No. 11, since the pressure was high, the orientation of the crystal grains was disturbed, the resistivity increased, and the figure of merit decreased.
【００３７】比較例No.１２は圧力が低いため、焼結不
十分で比抵抗が大きくなった。このため、性能指数が小
さくなった。In Comparative Example No. 12, since the pressure was low, the sintering was insufficient and the specific resistance increased. Therefore, the figure of merit decreased.
【００３８】[0038]
【発明の効果】以上詳述したように本発明においては、
結晶粒の配向性が乱れない条件でホットプレスにより固
化形成することにより、比抵抗が小さく、高い性能指数
を得ることができる。また、このようにして製造された
熱電材料は比抵抗が小さいため、低消費電力を必要とす
るデバイスに好適である。As described in detail above, in the present invention,
By solidifying and forming by hot pressing under the condition that the orientation of crystal grains is not disturbed, the specific resistance is small and a high figure of merit can be obtained. Further, the thermoelectric material manufactured in this manner has a small specific resistance, and thus is suitable for a device requiring low power consumption.
【図１】 縦軸に圧力、横軸に温度をとり、本発明の実
施例に係るホットプレス条件の範囲を示すグラフ図であ
る。FIG. 1 is a graph showing a range of hot pressing conditions according to an embodiment of the present invention, with pressure on the vertical axis and temperature on the horizontal axis.
Ｄ；領域 D; area
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） // Ｂ２２Ｆ 3/14 Ｂ２２Ｆ 3/14 Ｄ (72)発明者 堀尾 裕磨 静岡県浜松市中沢町10番１号 ヤマハ株式 会社内 (72)発明者 星 俊治 静岡県浜松市中沢町10番１号 ヤマハ株式 会社内 Ｆターム(参考） 4K017 AA04 BA10 BB18 DA01 EA03 EC02 4K018 AA40 BA20 BC01 EA02 KA32──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 7 Identification symbol FI theme coat ゛ (Reference) // B22F 3/14 B22F 3/14 D (72) Inventor Hiroma Horio 10th Nakazawacho, Hamamatsu City, Shizuoka Prefecture No. 1 Yamaha Corporation (72) Inventor Shunji Hoshi 10-1 Nakazawa-cho, Hamamatsu-shi, Shizuoka Prefecture F-term (reference) 4K017 AA04 BA10 BB18 DA01 EA03 EC02 4K018 AA40 BA20 BC01 EA02 KA32
Claims (7)
少なくとも１種の元素と、Ｔｅ及びＳｅからなる群から
選択された少なくとも１種の元素とを含有する原料を液
体急冷法により薄膜又は粉末にする工程と、これにより
得られた薄膜又は粉末の結晶粒の配向性が乱れない条件
でホットプレスにより固化成形する工程と、を有するこ
とを特徴とする熱電材料の製造方法。A thin film or powder of a raw material containing at least one element selected from the group consisting of Bi and Sb and at least one element selected from the group consisting of Te and Se by a liquid quenching method. And a step of solidifying and molding by hot pressing under conditions where the orientation of the crystal grains of the thin film or powder obtained thereby is not disturbed.
少なくとも１種の元素と、Ｔｅ及びＳｅからなる群から
選択された少なくとも１種の元素とを含有する原料を液
体急冷法により薄膜又は粉末にする工程と、これにより
得られた薄膜又は粉末を温度をＴ（℃）、圧力をＰ（ｋ
ｇｆ／ｃｍ2）とするとき、前記Ｔが２００≦Ｔ≦４０
０のとき、前記Ｐは−（３９／２０）×Ｔ＋７９０≦Ｐ
＜４００であり、前記Ｔが４００＜Ｔ≦６００のとき、
前記Ｐは１０≦Ｐ＜４００である条件でホットプレスに
より固化成形する工程と、を有することを特徴とする熱
電材料の製造方法。2. A thin film or powder of a raw material containing at least one element selected from the group consisting of Bi and Sb and at least one element selected from the group consisting of Te and Se by a liquid quenching method. And the temperature of the obtained thin film or powder is set to T (° C.) and the pressure is set to P (k).
gf / cm 2 ), T is 200 ≦ T ≦ 40
When 0, the P is − (39/20) × T + 790 ≦ P
<400, and when T is 400 <T ≦ 600,
A step of solidifying and molding by hot pressing under the condition that P satisfies 10 ≦ P <400.
Ａｇ及びＣｕからなる群から選択された少なくとも１種
の元素を含有することを特徴とする請求項１又は２に記
載の熱電材料の製造方法。3. The raw material further comprises I, Cl, Hg, Br,
The method for producing a thermoelectric material according to claim 1, wherein the thermoelectric material contains at least one element selected from the group consisting of Ag and Cu.
程は、加熱時間をｔとするとき、前記ｔは５乃至１５０
分であることを特徴とする請求項１乃至３のいずれか１
項に記載の熱電材料の製造方法。4. The step of solidifying and molding by the hot press is such that when the heating time is t, the t is 5 to 150.
4. The method according to claim 1, wherein
The method for producing a thermoelectric material according to the above item.
れた少なくとも１種の元素と、Ｔｅ及びＳｅからなる群
から選択された少なくとも１種の元素とを含有する原料
を液体急冷法により薄膜又は粉末にする工程の後工程と
して、前記薄膜又は粉末を粉砕する工程を有することを
特徴とする請求項１乃至４のいずれか１項に記載の熱電
材料の製造方法。5. A thin film or a raw material containing at least one element selected from the group consisting of Bi and Sb and at least one element selected from the group consisting of Te and Se by a liquid quenching method. The method for producing a thermoelectric material according to any one of claims 1 to 4, further comprising a step of pulverizing the thin film or the powder as a step subsequent to the step of forming the powder.
れた少なくとも１種の元素と、Ｔｅ及びＳｅからなる群
から選択された少なくとも１種の元素とを含有する原料
を液体急冷法により薄膜又は粉末にする工程の後工程と
して、前記薄膜又は粉末を水素雰囲気中で加熱する工程
を有することを特徴とする請求項１乃至４のいずれか１
項に記載の熱電材料の製造方法。6. A thin film or a raw material containing at least one element selected from the group consisting of Bi and Sb and at least one element selected from the group consisting of Te and Se by a liquid quenching method. 5. The method according to claim 1, further comprising a step of heating the thin film or the powder in a hydrogen atmosphere as a step subsequent to the step of forming the powder.
The method for producing a thermoelectric material according to the above item.
程として、水素雰囲気中で加熱する工程を有することを
特徴とする請求項５に記載の熱電材料の製造方法。7. The method for producing a thermoelectric material according to claim 5, further comprising a step of heating in a hydrogen atmosphere as a step subsequent to the step of pulverizing the thin film or the powder.
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|---|---|---|---|
| JP13777799A JP3575332B2 (en) | 1999-05-18 | 1999-05-18 | Thermoelectric material and method for manufacturing the same |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1333093C (en) * | 2005-11-17 | 2007-08-22 | 钢铁研究总院 | Preparation method of bismuth-tollurium base thromoelectric alloy |
| US20120018681A1 (en) * | 2010-07-22 | 2012-01-26 | Toyota Motor Engineering & Manufacturing North America, Inc. | Process for optimum thermoelectric properties |
| US8692103B2 (en) | 2003-05-08 | 2014-04-08 | Ihi Corporation | Thermoelectric semiconductor material, thermoelectric semiconductor element using thermoelectric semiconductor material, thermoelectric module using thermoelectric semiconductor element and manufacturing method for same |
-
1999
- 1999-05-18 JP JP13777799A patent/JP3575332B2/en not_active Expired - Lifetime
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8692103B2 (en) | 2003-05-08 | 2014-04-08 | Ihi Corporation | Thermoelectric semiconductor material, thermoelectric semiconductor element using thermoelectric semiconductor material, thermoelectric module using thermoelectric semiconductor element and manufacturing method for same |
| US8884152B2 (en) | 2003-05-08 | 2014-11-11 | Ihi Corporation | Thermoelectric semiconductor material, thermoelectric semiconductor element using thermoelectric semiconductor material, thermoelectric module using thermoelectric semiconductor element and manufacturing method for same |
| CN1333093C (en) * | 2005-11-17 | 2007-08-22 | 钢铁研究总院 | Preparation method of bismuth-tollurium base thromoelectric alloy |
| US20120018681A1 (en) * | 2010-07-22 | 2012-01-26 | Toyota Motor Engineering & Manufacturing North America, Inc. | Process for optimum thermoelectric properties |
| US8435429B2 (en) * | 2010-07-22 | 2013-05-07 | Toyota Motor Engineering & Manufacturing North America, Inc. | Process for optimum thermoelectric properties |
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| Publication number | Publication date |
|---|---|
| JP3575332B2 (en) | 2004-10-13 |
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