JPH02219285A - Thermoelectric material - Google Patents
Thermoelectric materialInfo
- Publication number
- JPH02219285A JPH02219285A JP1039734A JP3973489A JPH02219285A JP H02219285 A JPH02219285 A JP H02219285A JP 1039734 A JP1039734 A JP 1039734A JP 3973489 A JP3973489 A JP 3973489A JP H02219285 A JPH02219285 A JP H02219285A
- Authority
- JP
- Japan
- Prior art keywords
- carbide
- boron
- silicon
- silicon carbide
- seebeck coefficient
- 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 18
- 229910052580 B4C Inorganic materials 0.000 claims abstract description 19
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910010271 silicon carbide Inorganic materials 0.000 claims abstract description 19
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000002131 composite material Substances 0.000 claims abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 9
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 6
- 239000010703 silicon Substances 0.000 claims abstract description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052796 boron Inorganic materials 0.000 claims abstract description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000002075 main ingredient Substances 0.000 abstract 2
- 230000000694 effects Effects 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000005049 silicon tetrachloride Substances 0.000 description 4
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 230000005678 Seebeck effect Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- -1 chalcogenide compounds Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 description 2
- KPZGRMZPZLOPBS-UHFFFAOYSA-N 1,3-dichloro-2,2-bis(chloromethyl)propane Chemical compound ClCC(CCl)(CCl)CCl KPZGRMZPZLOPBS-UHFFFAOYSA-N 0.000 description 1
- 229910002665 PbTe Inorganic materials 0.000 description 1
- 230000005679 Peltier effect Effects 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910003465 moissanite Inorganic materials 0.000 description 1
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- OCGWQDWYSQAFTO-UHFFFAOYSA-N tellanylidenelead Chemical compound [Pb]=[Te] OCGWQDWYSQAFTO-UHFFFAOYSA-N 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- 238000002230 thermal chemical vapour deposition Methods 0.000 description 1
- 230000005676 thermoelectric effect Effects 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、太陽エネルギー等を始めとする熱エネルギー
をゼーベック効果を利用して、電気エネルギーに変換、
あるいは、ベルチェ効果による電子冷却を行う熱電材料
に関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention utilizes the Seebeck effect to convert thermal energy such as solar energy into electrical energy.
Alternatively, the present invention relates to a thermoelectric material that performs electronic cooling using the Beltier effect.
この発明は、太陽エネルギー等の熱エネルギーをゼーベ
ック効果により、電気エネルギーに変換する熱電材料、
また、ベルチェ効果による電子冷却用材料として、炭化
ホウ素と炭化ケイ素を主成分とし、不可避的成分として
、遊離炭素、ホウ素およびケイ素等から成る複合材料を
用いることにより、高性能の熱電材料を提供するもので
ある。This invention relates to a thermoelectric material that converts thermal energy such as solar energy into electrical energy by the Seebeck effect;
In addition, as a material for electronic cooling using the Beltier effect, a composite material containing boron carbide and silicon carbide as main components and free carbon, boron, silicon, etc. as inevitable components is used to provide a high-performance thermoelectric material. It is something.
従来、熱電材料としてＰｂＴｅ、Ｂ ｉｚ Ｔｅ３等の
化合物が用いられていた。また、ＳｉＣやＢ４Ｃなどの
ケイ素やホウ素の化合物も性能が高いことが知られてい
た。Conventionally, compounds such as PbTe and B iz Te3 have been used as thermoelectric materials. It was also known that silicon and boron compounds such as SiC and B4C have high performance.
熱電材料は、ゼーベツク係数が大きく、電気抵抗が低く
、熱伝導率が低いものが優れている。Thermoelectric materials are best if they have a large Seebeck coefficient, low electrical resistance, and low thermal conductivity.
一般に、テルルやセレン等のいわゆるカルコゲナイド化
合物を熱電材料として用いる場合、優れた特性を有して
いるが、３００℃程度以上の温度になると、その特性を
失ってしまうという問題点を有していた。In general, when so-called chalcogenide compounds such as tellurium and selenium are used as thermoelectric materials, they have excellent properties, but they have the problem that they lose their properties when the temperature exceeds about 300°C. .
一方、ＳｉＣでは耐熱性及び熱起電力においては優れた
特性を示すが、熱電材料として重要な電気抵抗が高いと
いう欠点をもっていた。また、Ｂ４Ｃでは、電気抵抗と
いう点では優れた特性を有しているが、ＳｉＣに比べ、
ゼーベック係数の面で劣るという欠点があった。On the other hand, although SiC exhibits excellent properties in terms of heat resistance and thermoelectromotive force, it has the drawback of high electrical resistance, which is important as a thermoelectric material. In addition, B4C has excellent characteristics in terms of electrical resistance, but compared to SiC,
It had the disadvantage of being inferior in terms of Seebeck coefficient.
上記の問題点を解決するために、炭化ホウ素と炭化ケイ
素を主成分とし、不可避的成分として遊離炭素、ホウ素
およびケイ素等から成る複合材料を熱電材料として用い
る。In order to solve the above problems, a composite material containing boron carbide and silicon carbide as main components and free carbon, boron, silicon, etc. as inevitable components is used as a thermoelectric material.
上記のように、炭化ホウ素と炭化ケイ素を主成分とする
複合材料を用いることにより、高温においても高い性能
指数を有する熱電材料を提供することが出来る。As described above, by using a composite material containing boron carbide and silicon carbide as main components, it is possible to provide a thermoelectric material that has a high figure of merit even at high temperatures.
すなわち、炭化ホウ素と炭化ケイ素を複合化することに
より、再化合物の優れた特性を引き出すことが出来るの
である。That is, by combining boron carbide and silicon carbide, it is possible to bring out the excellent properties of the recombined compound.
〔実施例−１〕
本発明の実施例として、炭化ホウ素と炭化ケイ素の複合
材料の製造方法としてＣＶＤ法を例にあげて説明する。[Example-1] As an example of the present invention, a CVD method will be described as an example of a method for manufacturing a composite material of boron carbide and silicon carbide.
第１図は、本発明である炭化ホウ素と炭化ケイ素の複合
材料を作製するための直接加熱方式ＣＶＤ装置の縦断面
図である。FIG. 1 is a longitudinal sectional view of a direct heating type CVD apparatus for producing a composite material of boron carbide and silicon carbide according to the present invention.
まず、真空槽１を１０−３Ｔｏｒｒまで真空排気した後
、真空槽１内の圧力が１００ Ｔｏｒｒになるように水
素四塩化ケイ素、三塩化ホウ素およびメタンを導入した
。この時、四塩化ケイ素は水素ガスをキャリヤーガスと
して用い、液体の四塩化ケイ素をバブリングにより気化
することにより導入した。なお、各々の総流量は下記の
通りとした。また、基板であるカーボン基板２には、温
度が１６００℃になるように交流電流を流した。First, the vacuum chamber 1 was evacuated to 10 −3 Torr, and then hydrogen silicon tetrachloride, boron trichloride, and methane were introduced so that the pressure inside the vacuum chamber 1 was 100 Torr. At this time, silicon tetrachloride was introduced by vaporizing liquid silicon tetrachloride by bubbling, using hydrogen gas as a carrier gas. In addition, each total flow rate was as follows. Further, an alternating current was passed through the carbon substrate 2 as a substrate so that the temperature reached 1600°C.
（ガス流量条件）
水素 ・・・ １０００ｃｃ／ｍｉｎ四塩化ケ
イ素 ・・・ ５０ｃｃ／ｍｉｎ三塩化ホウ素 ・・
・ ２５０ｃｃ／ｍｉｎメタン ・・・５０Ｃ
Ｃ／Ｌｌｌｉｎ成膜を２時間行ったところ、カーボン基
板２上に膜厚０．５＋ｎ、組成がＢ ａ Ｃ２５ｍｏ１
％、Ｓ ｉ Ｃ７０ｍｏ１％、Ｃ５ｍｏ１％の複合材料
が形成された。(Gas flow conditions) Hydrogen...1000cc/min Silicon tetrachloride...50cc/min Boron trichloride...
・250cc/min methane...50C
When the C/Lllin film was formed for 2 hours, a film with a thickness of 0.5+n and a composition of B a C25 mo1 was formed on the carbon substrate 2.
%, S i C70mo1%, C5mo1% composite material was formed.
次に、カーボン基板を削り取り、生成物を板状にし、温
度に対する比抵抗率およびゼーベック係数の変化を測定
したものを第２図および第３図に示すが、高温における
熱電性能が極めて大きいものと推定できるものであった
。Next, the carbon substrate was scraped off, the product was made into a plate shape, and the changes in resistivity and Seebeck coefficient with respect to temperature were measured. Figures 2 and 3 show that the thermoelectric performance at high temperatures is extremely high. It was possible to estimate.
〔実施例−２〕
実施例１と同様のＣＶＤ装置を用い温度を１４００℃と
し、各々のガス流量を下記の通りにし、成膜を２時間行
ったところ、膜厚０．４鰭、組成がＢ４Ｃ１５ｍｏ１％
、Ｓ ｉ Ｃ８４ｍｏ１％、Ｃｌｍｏｌ％、さらに、第
２図および第３図のような温度に対する比抵抗とゼーベ
ック係数の変化を示す複合材料を得ることができた。[Example-2] Using the same CVD apparatus as in Example 1, the temperature was set to 1400°C, each gas flow rate was set as shown below, and film formation was performed for 2 hours. The film thickness was 0.4 fin and the composition was B4C15mo1%
, S i C84mol%, Clmol%, and a composite material exhibiting changes in resistivity and Seebeck coefficient with respect to temperature as shown in FIGS. 2 and 3 could be obtained.
（ガス流量条件）
水素 ・・・ １０００ｃｃ／ｍ１ｎ−塩化ホ
ウ素 ・・・ １００ｃｃ／ｍｉｎ四塩化ケイ素 ・
・・ ２００ｃｃ／ｍｉｎ・・・ １００ｃｃ／ｍ
ｉｎ
なお、同じＣＶＤ装置を用いて作製した炭化ケメタン
イ素（Ｓ ｉ Ｃ）単体と炭化ホウ素（Ｂ ａ Ｃ）の
ゼーベック係数と比抵抗の温度依存性を第２図および第
３図に示すが、実施例１および２にあげた炭化ホウ素と
炭化ケイ素の複合材料に比べ、炭化ケイ素単体では、ゼ
ーベック係数の絶対値では優れているものの、比抵抗の
面で、また、炭化ホウ素ではゼーベック係数および比抵
抗のいずれの面においても劣っていた。(Gas flow conditions) Hydrogen...1000cc/min-Boron chloride...100cc/minSilicon tetrachloride
... 200cc/min... 100cc/m
In Figures 2 and 3 show the temperature dependence of the Seebeck coefficient and resistivity of kemetane carbide (S i C) and boron carbide (B a C), which were produced using the same CVD equipment. Compared to the boron carbide and silicon carbide composite materials listed in Examples 1 and 2, silicon carbide alone is superior in terms of the absolute value of the Seebeck coefficient, but boron carbide has a lower Seebeck coefficient and ratio. It was inferior in both aspects of resistance.
この発明によれば、室温から高温において、優れた熱電
作用を有する材料を提供することができる。すなわち、
ゼーベック係数の大きい炭化ホウ素と炭化ケイ素を複合
することにより、ゼーベック係数は、そのまま高く維持
することができ、抵抗値を炭化ケイ素に比べ、数ケタ下
げることができ、ゼーベック係数においては炭化ホウ素
より大きくすることができた。According to the present invention, it is possible to provide a material that has excellent thermoelectric effect from room temperature to high temperature. That is,
By combining boron carbide, which has a large Seebeck coefficient, with silicon carbide, the Seebeck coefficient can be maintained as high as it is, and the resistance value can be lowered by several orders of magnitude compared to silicon carbide, and the Seebeck coefficient is larger than that of boron carbide. We were able to.
この材料の優れた熱電作用を利用することにより、太陽
エネルギーなどの熱エネルギーをゼーベック効果により
電気エネルギーに効率良く変換できる、一方、ペルチェ
効果による電子冷却効果も期待でき、ＩＣ用セラミック
ス基板の冷却や無振動冷却装置などの冷却装置用材料と
して利用されることが期待できる。By utilizing the excellent thermoelectric properties of this material, it is possible to efficiently convert thermal energy such as solar energy into electrical energy through the Seebeck effect, while electronic cooling effects due to the Peltier effect can also be expected, which can be used to cool ceramic substrates for ICs. It is expected that it will be used as a material for cooling devices such as vibration-free cooling devices.
なお、実施例では本発明である炭化ホウ素と炭化ケイ素
の複合材料をいわゆる熱ＣＶＤにより作製したが、その
他の方法、たとえば、−船釣な焼結法や反応焼結法、さ
らに、プラズマＣＶＤ法。In the examples, the composite material of boron carbide and silicon carbide of the present invention was produced by so-called thermal CVD, but other methods, such as - sintering method, reaction sintering method, and plasma CVD method .
ＰＶＤ法などの作製法なども考えられ、同様な効果が得
られることが期待できることは言うまでもない。It goes without saying that manufacturing methods such as the PVD method are also conceivable and can be expected to produce similar effects.
１・・・真空槽 ２・・・カーボン基板 以上1...Vacuum chamber 2...Carbon substrate that's all
Claims (1)
して遊離炭素、ホウ素およびケイ素等を含有する複合材
料を用いることを特徴とする熱電材料。A thermoelectric material characterized by using a composite material whose main components are boron carbide and silicon carbide, and which also contain free carbon, boron, silicon, etc. as inevitable components.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1039734A JP2549307B2 (en) | 1989-02-20 | 1989-02-20 | Thermoelectric material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1039734A JP2549307B2 (en) | 1989-02-20 | 1989-02-20 | Thermoelectric material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02219285A true JPH02219285A (en) | 1990-08-31 |
| JP2549307B2 JP2549307B2 (en) | 1996-10-30 |
Family
ID=12561203
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1039734A Expired - Fee Related JP2549307B2 (en) | 1989-02-20 | 1989-02-20 | Thermoelectric material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2549307B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003017389A3 (en) * | 2001-08-13 | 2003-04-10 | Motorola Inc | High performance thermoelectric material |
| WO2003069744A1 (en) * | 2002-02-14 | 2003-08-21 | Infineon Technologies Ag | Optoelectronic component with a peltier cooler |
| JP2008069771A (en) * | 2006-09-13 | 2008-03-27 | Caterpillar Inc | Thermoelectric system |
-
1989
- 1989-02-20 JP JP1039734A patent/JP2549307B2/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003017389A3 (en) * | 2001-08-13 | 2003-04-10 | Motorola Inc | High performance thermoelectric material |
| US6677515B2 (en) | 2001-08-13 | 2004-01-13 | Motorola, Inc. | High performance thermoelectric material and method of fabrication |
| WO2003069744A1 (en) * | 2002-02-14 | 2003-08-21 | Infineon Technologies Ag | Optoelectronic component with a peltier cooler |
| JP2008069771A (en) * | 2006-09-13 | 2008-03-27 | Caterpillar Inc | Thermoelectric system |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2549307B2 (en) | 1996-10-30 |
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