JPH11279605A - Thermoelectric semiconductor material and production thereof - Google Patents
Thermoelectric semiconductor material and production thereofInfo
- Publication number
- JPH11279605A JPH11279605A JP10347593A JP34759398A JPH11279605A JP H11279605 A JPH11279605 A JP H11279605A JP 10347593 A JP10347593 A JP 10347593A JP 34759398 A JP34759398 A JP 34759398A JP H11279605 A JPH11279605 A JP H11279605A
- Authority
- JP
- Japan
- Prior art keywords
- tube
- bismuth
- powder
- semiconductor material
- thermoelectric semiconductor
- 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.)
- Granted
Links
- 239000000463 material Substances 0.000 title claims abstract description 19
- 239000004065 semiconductor Substances 0.000 title claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 title description 5
- 239000000843 powder Substances 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 239000006104 solid solution Substances 0.000 claims abstract description 13
- 239000012535 impurity Substances 0.000 claims abstract description 7
- 238000005245 sintering Methods 0.000 claims abstract description 7
- 239000002245 particle Substances 0.000 claims description 13
- PDYNJNLVKADULO-UHFFFAOYSA-N tellanylidenebismuth Chemical compound [Bi]=[Te] PDYNJNLVKADULO-UHFFFAOYSA-N 0.000 claims description 5
- 238000007731 hot pressing Methods 0.000 claims 2
- 125000005843 halogen group Chemical group 0.000 claims 1
- 238000001816 cooling Methods 0.000 abstract description 15
- 229910052797 bismuth Inorganic materials 0.000 abstract description 10
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 abstract description 10
- 238000000034 method Methods 0.000 abstract description 8
- 239000010453 quartz Substances 0.000 abstract description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 5
- XSOKHXFFCGXDJZ-UHFFFAOYSA-N telluride(2-) Chemical compound [Te-2] XSOKHXFFCGXDJZ-UHFFFAOYSA-N 0.000 abstract description 5
- 238000010438 heat treatment Methods 0.000 abstract description 3
- 238000003756 stirring Methods 0.000 abstract description 3
- KWQLUUQBTAXYCB-UHFFFAOYSA-K antimony(3+);triiodide Chemical compound I[Sb](I)I KWQLUUQBTAXYCB-UHFFFAOYSA-K 0.000 abstract description 2
- 239000011261 inert gas Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 abstract description 2
- FBGGJHZVZAAUKJ-UHFFFAOYSA-N bismuth selenide Chemical compound [Se-2].[Se-2].[Se-2].[Bi+3].[Bi+3] FBGGJHZVZAAUKJ-UHFFFAOYSA-N 0.000 abstract 1
- 239000013078 crystal Substances 0.000 description 14
- OMEPJWROJCQMMU-UHFFFAOYSA-N selanylidenebismuth;selenium Chemical compound [Se].[Bi]=[Se].[Bi]=[Se] OMEPJWROJCQMMU-UHFFFAOYSA-N 0.000 description 12
- 238000010586 diagram Methods 0.000 description 5
- 238000005204 segregation Methods 0.000 description 3
- 239000011669 selenium Substances 0.000 description 3
- 238000005476 soldering Methods 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000010587 phase diagram Methods 0.000 description 2
- 229910052711 selenium Inorganic materials 0.000 description 2
- 229910000679 solder Inorganic materials 0.000 description 2
- 229910052714 tellurium Inorganic materials 0.000 description 2
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 230000005679 Peltier effect Effects 0.000 description 1
- 230000005678 Seebeck effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003574 free electron Substances 0.000 description 1
- 238000002194 freeze distillation Methods 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Landscapes
- Powder Metallurgy (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、熱電半導体材料および
その製造方法に関する。The present invention relates to a thermoelectric semiconductor material and a method for producing the same.
【０００２】[0002]
【従来技術およびその問題点】ペルチェ効果、あるいは
エッチングスハウゼン効果を利用した電子冷却素子、あ
るいはゼーベック効果を利用した熱電発電素子は、構造
が簡単でかつ取扱いが容易で安定な特性を維持できるこ
とから、広範囲にわたる利用が注目されている。2. Description of the Related Art A thermoelectric generator using the Peltier effect or the Etching-Shausen effect or a thermoelectric generator using the Seebeck effect has a simple structure, is easy to handle, and can maintain stable characteristics. , Widespread use is attracting attention.
【０００３】ところで、従来、超電導素子の冷却には極
低温が必要であるため液体ヘリウムによる冷却しか方法
がなく、冷却コストおよび使用場所等の面で制限が多か
った。ところが最近、超電導材料の目ざましい発達によ
り臨界温度の高いものが得られるようになり、必要温度
が上昇し、電子冷却素子による冷却で、超電導素子を駆
動できるようになってきている。Heretofore, cooling of a superconducting element requires an extremely low temperature, so there is only a method of cooling with liquid helium, and there have been many limitations in terms of cooling cost, use place, and the like. However, recently, a remarkable development of a superconducting material has made it possible to obtain a material having a high critical temperature, the required temperature has been increased, and the superconducting element can be driven by cooling by an electronic cooling element.
【０００４】この電子冷却に用いる熱電材料のうちｎ型
半導体として用いられる代表的なものに、テルル化ビス
マス（Ｂi2Ｔe3）に５モル％のセレン化ビスマス（Ｂi2
Ｓe3）を添加すると共に電子濃度の調整のための不純物
を添加した溶液に、温度勾配を与えながら溶液全体の温
度を除々に引き下げるいわゆるノーマルフリージング法
により形成される単結晶インゴットもしくは結晶粒径の
大きい多結晶インゴットがある。Among the thermoelectric materials used for the electronic cooling, a typical one used as an n-type semiconductor is bismuth telluride (Bi2Te3) with 5 mol% of bismuth selenide (Bi2
A single crystal ingot or a crystal having a large grain size formed by a so-called normal freezing method in which a temperature gradient is gradually applied to a solution to which Se3) is added and an impurity for adjusting an electron concentration is added. There are polycrystalline ingots.
【０００５】ところで、熱電材料の良否は、物質固有の
定数である熱起電力αと電気伝導率σと熱伝導率Ｋによ
って表わされる性能指数Ｚ（＝α2σ／Ｋ）の大小で決
まる。The quality of a thermoelectric material is determined by the magnitude of a figure of merit Z (= α2σ / K) represented by thermoelectric power α, electric conductivity σ, and heat conductivity K, which are constants inherent to the material.
【０００６】すなわち、Ｚが大きいほど性能が良いわけ
であるが、テルル化ビスマス（Ｂi2Ｔe3），セレン化ビ
スマス（Ｂi2Ｓe3）および両者の固溶体について多くの
研究報告例が発表されている。その一例を図３（ａ）お
よび（ｂ）に示す。この図からも明らかなように、テル
ル化ビスマスとセレン化ビスマスのモル比が８０：２０
ないし７５：２５のとき熱伝導率Ｋが最小となりα2σ
および自由電子の質量に対する電子の有効質量の比ｍ*
／ｍが大きくなる。これは、テルル化ビスマス、セレン
化ビスマス両者の結晶対称性が同じで格子定数がわずか
に異なることにより、固溶体にすると結晶にわずかな歪
が生じ、それによってフォノンの散乱、電子の有効質量
ｍ*の変化が生じるためと考えられている。[0006] That is, although the higher the Z, the better the performance, many research reports have been published on bismuth telluride (Bi2Te3), bismuth selenide (Bi2Se3) and solid solutions of both. One example is shown in FIGS. 3 (a) and 3 (b). As is clear from this figure, the molar ratio of bismuth telluride to bismuth selenide is 80:20.
To 75:25, the thermal conductivity K becomes minimum and α2σ
And the ratio of the effective mass of electrons to the mass of free electrons, m *
/ M increases. This is because both bismuth telluride and bismuth selenide have the same crystal symmetry and slightly different lattice constants, so that a solid solution causes a slight strain in the crystal, which causes scattering of phonons, effective mass of electrons m * It is thought that the change occurs.
【０００７】しかしながら、図４に示す如く固溶体の状
態図から明らかなように、セレン化ビスマスの含有率を
高めると偏析が起り、一本の単結晶インゴットの中で目
的とする組成の部分はごくわずかしか得られないという
問題があった。現在の技術では、セレン化ビスマスの含
有率を５％以上にしたものを工業製品として得るのは不
可能な状態であった。However, as is apparent from the phase diagram of the solid solution as shown in FIG. 4, when the content of bismuth selenide is increased, segregation occurs, and the portion of the target composition in one single crystal ingot is very small. There was a problem that only a small amount could be obtained. With the current technology, it was impossible to obtain a product having a bismuth selenide content of 5% or more as an industrial product.
【０００８】更に、テルル化ビスマス、セレン化ビスマ
スの結晶は著しい劈開性を有しており、インゴットから
熱電素子を得るためのスライシング、ダイシング工程等
を経ると、割れや欠けの為に歩留りが極めて低くなるこ
とが実用化をはばむ大きな問題となっていた。Further, the crystals of bismuth telluride and bismuth selenide have remarkable cleavability, and after slicing or dicing for obtaining a thermoelectric element from an ingot, the yield is extremely high due to cracking or chipping. The lowering has been a major problem that will delay practical application.
【０００９】一方、結晶としてではなく、粉末焼結体と
して用いると劈開性の問題はなくなるが、焼結密度が上
がらず、半田付けを行なうと内部に半田がしみ込み性能
低下を引き起こすという問題がある。On the other hand, the use of a powdered sintered body instead of a crystal eliminates the problem of cleavage, but the sintering density does not increase, and the solder penetrates into the interior when soldering, causing a problem of reduced performance. is there.
【００１０】更に、粉末の場合、ドーピング制御が困難
であり一定量の不純物を添加してもキャリア濃度が一定
にならないという問題があった。Further, in the case of powder, there is a problem that it is difficult to control doping, and even if a certain amount of impurity is added, the carrier concentration is not constant.
【００１１】本発明は、前記実情に鑑みてなされたもの
で、ドーピング制御が容易で製造歩留りの高い熱電半導
体材料を提供することを目的とする。The present invention has been made in view of the above circumstances, and has as its object to provide a thermoelectric semiconductor material which can be easily controlled for doping and has a high production yield.
【００１２】[0012]
【課題を解決するための手段】そこで本発明では、粒径
の均一なテルル化ビスマス−セレン化ビスマス固溶体粉
末からなる粉末焼結体によって熱電半導体材料を構成し
ている。Accordingly, in the present invention, a thermoelectric semiconductor material is constituted by a powder sintered body composed of a bismuth telluride-bismuth selenide solid solution powder having a uniform particle size.
【００１３】また、本発明の方法では、目的とする組成
となるようにビスマス、テルル、セレンを加熱溶融せし
めた後、急冷してインゴットを形成してこれを粉砕し、
粒径を揃えた後、加圧焼結するようにしている。In the method of the present invention, bismuth, tellurium, and selenium are heated and melted so as to obtain a desired composition, and then quenched to form an ingot, which is pulverized.
After the particle diameters are adjusted, pressure sintering is performed.
【００１４】[0014]
【作用】本発明では、単結晶ではなく、粉末焼結体で構
成されているため、組成比を自由に選択でき、性能指数
Ｚの高いものを得ることができる。又粒径を揃えること
により、ドーピング制御が容易となる。これは、粒径が
揃うと粒界の分布も均一となり、粒界から発生すると考
えられる電子も一定となるため、電子濃度の再現性もよ
くなるものと考えられる。According to the present invention, the composition is not a single crystal but a powder sintered body, so that the composition ratio can be freely selected and a high figure of merit Z can be obtained. Further, by adjusting the particle diameter, doping control becomes easy. This is presumably because, when the particle diameters are uniform, the distribution of the grain boundaries becomes uniform, and electrons considered to be generated from the grain boundaries become constant, so that the reproducibility of the electron concentration is improved.
【００１５】また、粒径を揃えることにより、焼結密度
が上がり、半田付工程においても半田のしみ込みによる
性能低下もない。Further, by arranging the particle diameters, the sintering density is increased, and the performance does not decrease due to the penetration of the solder in the soldering step.
【００１６】加えて、単結晶あるいは多結晶のインゴッ
トをそのまま用いた場合らに比べ、割れ等による製造歩
留りの低下も大幅に低減される。In addition, as compared with a case where a single crystal or polycrystalline ingot is used as it is, a decrease in manufacturing yield due to cracks or the like is greatly reduced.
【００１７】[0017]
【実施例】以下、本発明の実施例について、図面を参照
しつつ詳細に説明する。Embodiments of the present invention will be described below in detail with reference to the drawings.
【００１８】まず、ビスマスＢｉ 313.50ｇ、テルルＴ
ｅ 272.77ｇ、セレンＳｅ 8.883ｇを秤量し、更にキャ
リア濃度を調整するためにヨウ化アンチモン0.0837ｇ
（0.02モルパーセント）を添加し、この混合物を石英管
内に投入した後、真空ポンプによって管内の空気を排
気，封入する。First, 313.50 g of bismuth Bi, tellurium T
272.77 g of e and 8.883 g of selenium Se, and 0.0837 g of antimony iodide for further adjusting the carrier concentration
(0.02 mol%), and the mixture is charged into a quartz tube, and then the air in the tube is evacuated and sealed by a vacuum pump.
【００１９】この管を６５０℃に加熱し３時間にわたり
石英管内を撹拌しつつ化合させた後、凝固点直下である
５６０℃の領域に石英管を移動し急冷する。After heating the tube to 650 ° C. and stirring the quartz tube for 3 hours while stirring, the quartz tube is moved to a region of 560 ° C. immediately below the freezing point and rapidly cooled.
【００２０】次に、この急冷インゴットをスタンプミ
ル、ボールミル等で粉砕した後、２００メッシュおよび
４００メッシュの篩にかけ４００メッシュの篩上に残っ
たものを選び、粒径３７〜７４μｍ程度の粉末に揃え
る。Next, the quenched ingot is pulverized by a stamp mill, a ball mill, or the like, and then sieved through a 200-mesh or 400-mesh sieve. .
【００２１】このようにして粒径の揃えられた粉末を真
空中または不活性ガス中でホットプレス法によりカーボ
ンダイスを用いてホットプレスし、粉末焼結体を形成す
る。The powder having a uniform particle size is hot-pressed in a vacuum or an inert gas by a hot press method using a carbon die to form a powder sintered body.
【００２２】この後、この粉末焼結体を３ミリ角６ミリ
長のチップに分断し、ｎ型のＢｉＴｅＳｅを形成する。Thereafter, the powder sintered body is divided into chips of 3 mm × 6 mm length to form n-type BiTeSe.
【００２３】このようにして形成されたｎ型のＢｉＴｅ
Ｓｅ１を、性能テストのために同寸法の単結晶ｐ型Ｂｉ
ＴｅＳｅ２と接続してｐ−ｎ素子対３を形成し、これを
図２に示す如く真空容器４内に設置する。ここで５は電
極としての銅板、６は水冷銅ブロック、７は絶縁部材、
８は電子循環恒温槽、９は定電流電源である。そして、
このｐ−ｎ素子対の発熱側の温度ＴH を２３℃に保ちつ
つｐ−ｎ素子対に電流を流し、冷却側の温度Ｔｃを測定
する。この冷却特性は図１の曲線ａ１に示す通りであ
り、最大温度差△Ｔmax＝ＴH−ＴC＝70.4℃を記録し
た。また、曲線ａ２には、このｐ−ｎ素子対の発熱側の
温度ＴH を３℃に保持したときの、冷却側の温度ＴC を
示す。The n-type BiTe thus formed is
Se1 was converted to single-crystal p-type Bi of the same size for performance testing.
A pn element pair 3 is formed by connecting with TeSe2, and this is set in a vacuum vessel 4 as shown in FIG. Here, 5 is a copper plate as an electrode, 6 is a water-cooled copper block, 7 is an insulating member,
8 is an electronic circulating thermostat, 9 is a constant current power supply. And
While maintaining the temperature TH on the heat generation side of the pn element pair at 23 ° C., a current is applied to the pn element pair, and the temperature Tc on the cooling side is measured. This cooling characteristic was as shown by the curve a1 in FIG. 1, and the maximum temperature difference ΔTmax = TH−TC = 70.4 ° C. was recorded. The curve a2 shows the cooling-side temperature TC when the temperature TH on the heating side of the pn element pair is maintained at 3 ° C.
【００２４】比較のために、ｎ型素子の方も単結晶Ｂｉ
ＴｅＳｅで形成したｐ−ｎ素子対についての同様の冷却
特性を測定した結果を曲線ｂ１に示す。この曲線ｂ１か
らも明らかなように最大温度差は△Ｔmax＝56.05℃とな
っている。又ｂ２は同様に発熱側の温度ＴH を３℃にし
たときの冷却側の温度ＴC を示す。これら曲線ａ１，ａ
２，ｂ１，ｂ２の比較からも本発明実施例のｎ型ＢｉＴ
ｅＳｅ（焼結体）によれば冷却性能の優れた熱電素子を
形成することが可能となることがわかる。For comparison, the n-type element is also a single crystal Bi
A curve b1 shows the result of measuring the same cooling characteristics of the pn element pair formed of TeSe. As is clear from the curve b1, the maximum temperature difference is ΔTmax = 56.05 ° C. Similarly, b2 indicates the cooling-side temperature TC when the heating-side temperature TH is set to 3 ° C. These curves a1, a
2, b1, b2 also shows that the n-type BiT
It can be seen that eSe (sintered body) makes it possible to form a thermoelectric element having excellent cooling performance.
【００２５】また、このｎ型焼結体は機械的強度も大き
く、半田付特性も良好であった。The n-type sintered body had high mechanical strength and good soldering characteristics.
【００２６】また、Ｂi2Ｔe3 ： Ｂi2Ｓe3＝ ９：１の
組成比で同様の実験を行なった場合、本発明の焼結体か
らなるｎ型ＢｉＴｅＳｅと、単結晶ｐ型ＢｉＴｅＳｅと
で構成したｐ−ｎ素子対の発熱側温度を２３℃にしたと
き最大温度差△Ｔmaxは６５℃であった。これによって
も冷却性能が優れていることがわかる。ここで、前述し
た組成のものよりも△Ｔmax が小さいのは、Ｂi2Ｔe3と
Ｂi2Ｓe3の組成比を変えたのにハロゲンの添加量を変え
なかったため、電子濃度の最適値からずれたためと考え
られる。（ここでセレン化ビスマスはｎ型、テルル化ビ
スマスはｐ型の材料であるため、セレン化ビスマスの比
率を増大せしめるにつれて、添加するドナー不純物を減
少させなければならない。）なお、本発明実施例の方法
においては、材料を石英管内で加熱溶融し化合せしめた
後、凝固点よりもわずかに低い温度まで急冷するという
方法をとっている。When a similar experiment was carried out with a composition ratio of Bi2Te3: Bi2Se3 = 9: 1, a pn device composed of an n-type BiTeSe made of the sintered body of the present invention and a single-crystal p-type BiTeSe was used. When the exothermic side temperature of the pair was 23 ° C., the maximum temperature difference ΔTmax was 65 ° C. This also shows that the cooling performance is excellent. Here, it is considered that the reason why ΔTmax is smaller than that of the above-described composition is that, although the composition ratio of Bi2Te3 and Bi2Se3 was changed, the addition amount of halogen was not changed, and the electron concentration deviated from the optimum value. (Because bismuth selenide is an n-type material and bismuth telluride is a p-type material, as the ratio of bismuth selenide is increased, the amount of donor impurities to be added must be reduced.) Incidentally, the examples of the present invention In the above method, the material is heated and melted in a quartz tube and combined, and then rapidly cooled to a temperature slightly lower than the freezing point.
【００２７】従来は偏析を逸れるため、常温程度まで急
冷するという方法がとられている。この場合、微結晶と
なるために粒界が増大し過ぎ、ドーピング制御が困難に
なることがあったが、本発明実施の方法によれば、適切
な粒度を得ることが可能となる。Conventionally, a method of rapidly cooling to about normal temperature has been adopted in order to avoid segregation. In this case, the grain boundaries are excessively increased due to the formation of microcrystals, so that doping control is sometimes difficult. However, according to the method of the present invention, it is possible to obtain an appropriate grain size.
【００２８】また、この粉末焼結体の組成比は、Ｂｉ2
（Ｔｅ1-X ＳｅX ）3 としたとき、0.05＜Ｘ＜0.3 とす
るのが望ましい。Ｘ＞0.3 であると偏析が起り、目的構
成のものは、わずかしかできず、0.05＞Ｘであると、熱
伝導率Ｋが大きくなり十分大きい性能指数Ｚを得ること
ができない。The composition ratio of the powder sintered body is Bi 2
When (Te1-x Sex) 3, it is preferable that 0.05 <X <0.3. If X> 0.3, segregation occurs, and only a small amount of the target composition can be formed. If 0.05> X, the thermal conductivity K increases and a sufficiently large figure of merit Z cannot be obtained.
【００２９】更に、キャリア濃度を調整するために添加
するハロゲンの量は１０20ｃｍ-3以下であるのが望まし
い。Further, the amount of halogen added for adjusting the carrier concentration is desirably 1020 cm-3 or less.
【００３０】更にまた、粉末焼結体中の粉末粒径を３７
〜７４μｍ程度に揃えたが、１０〜２００μｍの範囲内
で適宜領域を選択すればよい。１０μｍ以下であると、
粒界が非常に多くなるためにドーピング制御が困難とな
る上、粒界でのキャリアの散乱により移動度が低下する
ことにより、特性が低下する。また、粉末の凝集が起り
易くなり扱いが困難である。Further, the particle size of the powder in the powder sintered body is set to 37.
The range is set to about 74 μm, but an appropriate area may be selected within the range of 10 to 200 μm. When it is 10 μm or less,
Since the number of grain boundaries is very large, doping control becomes difficult, and the mobility is reduced due to scattering of carriers at the grain boundaries, so that the characteristics are deteriorated. In addition, the powder tends to agglomerate and is difficult to handle.
【００３１】また、２００μｍ以上であると、十分な機
械的強度および十分な焼結密度を得ることができない。On the other hand, if the thickness is 200 μm or more, sufficient mechanical strength and sufficient sintered density cannot be obtained.
【００３２】[0032]
【発明の効果】以上説明してきたように、本発明によれ
ば粒径の均一なテルル化ビスマス−セレン化ビスマス固
溶体の粉末焼結体から構成しているため、ドーピング制
御が容易で、性能指数が高く、製造歩留りの高い熱電半
導体を得ることが可能となる。As described above, according to the present invention, since the powdery sintered body of the bismuth telluride-bismuth selenide solid solution having a uniform particle diameter is used, the doping control is easy and the performance index is improved. And a thermoelectric semiconductor with a high production yield can be obtained.
【図１】本発明実施例のｎ型ＢｉＴｅＳｅを用いて形成
した熱電素子と単結晶のｎ型ＢｉＴｅＳｅを用いて形成
した熱電素子の冷却特性を示す比較図FIG. 1 is a comparison diagram showing cooling characteristics of a thermoelectric element formed using n-type BiTeSe and a thermoelectric element formed using single-crystal n-type BiTeSe according to an embodiment of the present invention.
【図２】同冷却特性の測定装置を示す図FIG. 2 is a diagram showing an apparatus for measuring the cooling characteristics.
【図３】図３（ａ）はＢi2Ｔe3とＢi2Ｓe3の組成比と性
能指数との関係を示す図で図３（ｂ）はＢi2Ｔe3とＢi2
Ｓe3の組成比と性能指数との関係を示す図FIG. 3A is a diagram showing the relationship between the composition ratio of Bi2Te3 and Bi2Se3 and the figure of merit, and FIG. 3B is a diagram showing the relationship between Bi2Te3 and Bi2.
Diagram showing the relationship between the composition ratio of Se3 and the figure of merit
【図４】固溶体の状態図FIG. 4 is a phase diagram of a solid solution.
１…ｎ型ＢｉＴｅＳｅ ２…単結晶ｐ型ＢｉＴｅＳｅ ３…熱電素子 ４…真空容器 DESCRIPTION OF SYMBOLS 1 ... n-type BiTeSe 2 ... single crystal p-type BiTeSe 3 ... thermoelectric element 4 ... vacuum container
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ // Ｃ２２Ｃ 12/00 Ｃ２２Ｃ 12/00 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 6 Identification code FI // C22C 12/00 C22C 12/00
Claims (5)
ス（Ｂi2Ｔe3）−セレン化ビスマス（Ｂi2Ｓe3）固溶体
粉末の粒径を１０〜２００ミクロンの範囲に均一化する
粒径調整工程と、 粒径の均一となった固溶体粉末をホットプレスにより焼
結せしめる焼結工程とを含むことを特徴とする熱電半導
体材料の製造方法。1. A particle size adjusting step for uniformizing the particle size of a bismuth telluride (Bi2Te3) -bismuth selenide (Bi2Se3) solid solution powder containing impurities of one conductivity type to a range of 10 to 200 microns. A sintering step of sintering the homogeneous solid solution powder by hot pressing.
テルル化ビスマス（Ｂi2Ｔe3）−セレン化ビスマス（Ｂ
i2Ｓe3）固溶体粉末を、ホットプレスにより焼結させた
粉末焼結体からなり、 前記固溶体の粒径が１０〜２００ミクロンの範囲にある
ことを特徴とする熱電半導体材料。2. Bismuth telluride (Bi2Te3) -bismuth selenide (B) having a uniform particle size and containing impurities of one conductivity type.
i2Se3) A thermoelectric semiconductor material comprising a powder sintered body obtained by sintering a solid solution powder by hot pressing, wherein the particle diameter of the solid solution is in the range of 10 to 200 microns.
クロンの範囲にあることを特徴とする特許請求の範囲第
２項記載の熱電半導体材料。3. The thermoelectric semiconductor material according to claim 2, wherein the particle diameter of said solid solution powder is in the range of 37 to 74 microns.
Ｓe x）3 (0.05<x<0.3)に示す組成を有するものである
ことを特徴とする特許請求の範囲第２項記載の熱電半導
体材料。4. The solid solution powder according to the following formula Bi2 (Te 1-x
3. The thermoelectric semiconductor material according to claim 2, wherein the thermoelectric semiconductor material has a composition represented by (Sex) 3 (0.05 <x <0.3).
ハロゲン原子であることを特徴とする特許請求の範囲第
２項記載の熱電半導体材料。5. The thermoelectric semiconductor material according to claim 2, wherein said impurity is a halogen atom added at 1020 cm −3 or less.
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|---|---|---|---|
| JP34759398A JP3278140B2 (en) | 1998-12-07 | 1998-12-07 | Thermoelectric semiconductor material and method of manufacturing the same |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34759398A JP3278140B2 (en) | 1998-12-07 | 1998-12-07 | Thermoelectric semiconductor material and method of manufacturing the same |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62192238A Division JPH0832588B2 (en) | 1987-07-31 | 1987-07-31 | Thermoelectric semiconductor material and manufacturing method thereof |
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| Publication Number | Publication Date |
|---|---|
| JPH11279605A true JPH11279605A (en) | 1999-10-12 |
| JP3278140B2 JP3278140B2 (en) | 2002-04-30 |
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ID=18391275
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|---|---|---|---|
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110002412A (en) * | 2019-04-22 | 2019-07-12 | 武汉科技大学 | A kind of preparation method of preferred orientation N-shaped bismuth telluride-base polycrystalline bulk thermoelectric material |
| CN114551706A (en) * | 2022-02-21 | 2022-05-27 | 北京航空航天大学 | P-type bismuth antimony selenide thermoelectric material and preparation method thereof |
-
1998
- 1998-12-07 JP JP34759398A patent/JP3278140B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110002412A (en) * | 2019-04-22 | 2019-07-12 | 武汉科技大学 | A kind of preparation method of preferred orientation N-shaped bismuth telluride-base polycrystalline bulk thermoelectric material |
| CN114551706A (en) * | 2022-02-21 | 2022-05-27 | 北京航空航天大学 | P-type bismuth antimony selenide thermoelectric material and preparation method thereof |
| CN114551706B (en) * | 2022-02-21 | 2022-10-21 | 北京航空航天大学 | P-type bismuth antimony selenide thermoelectric material and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| JP3278140B2 (en) | 2002-04-30 |
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