JPS6165487A - Manufacture of thermoelectric conversion element - Google Patents
Manufacture of thermoelectric conversion elementInfo
- Publication number
- JPS6165487A JPS6165487A JP59186416A JP18641684A JPS6165487A JP S6165487 A JPS6165487 A JP S6165487A JP 59186416 A JP59186416 A JP 59186416A JP 18641684 A JP18641684 A JP 18641684A JP S6165487 A JPS6165487 A JP S6165487A
- Authority
- JP
- Japan
- Prior art keywords
- glass tube
- powder
- type semiconductor
- thermoelectric conversion
- conversion element
- 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
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/01—Manufacture or treatment
Abstract
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、Ｎ型およびＰ型半導体対からなシ。[Detailed description of the invention] [Industrial application field] The present invention comprises a pair of N-type and P-type semiconductors.
ゼーベック効果を原理とする熱電気変換素子に関し１特
に該熱電気変換素子の製造方法に関する。The present invention relates to a thermoelectric conversion element based on the Seebeck effect, and particularly to a method for manufacturing the thermoelectric conversion element.
ゼーベ、り効果を原理とする熱電気変換素子の開発は古
くからなされている。最近、そのモジー−ル化の技術が
開発され、宇宙開発１海洋開発。Thermoelectric conversion elements based on the Seebe effect have been developed for a long time. Recently, the technology of making it into a module has been developed, and space development 1 ocean development.
廃熱発電、僻地用電源、温度用センサーなど多くの分野
で活発に利用され始めてきている。It has begun to be actively used in many fields such as waste heat power generation, power sources for remote areas, and temperature sensors.
従来の熱電気変換素子の製造方法によると１例えばけい
素化合物のＮ型半導体（ＦｅＣｏ）Ｓｉ２とＰ型半導体
（ＦｅＭｎ ）Ｓ ｉ ２からなる熱電気変換素子は、
まず通常Ｃｏ粉末を含むＦｅＳｉ２粉本とｒ Ｍｎ粉末
を含むＦ ｅ Ｓ ｉ ２粉体とを、Ｕ字型に冷間プレ
スで成型し。According to the conventional manufacturing method of a thermoelectric conversion element 1, for example, a thermoelectric conversion element made of silicon compound N-type semiconductor (FeCo)Si2 and P-type semiconductor (FeMn)Si2 is:
First, two FeSi powders containing normal Co powder and two FeSi powders containing rMn powder were cold pressed into a U-shape.
焼結する。この様にしてつくられた（ＦｅＣｏ）Ｓｉ２
と（ＦｅＭｎ ）Ｓ ｉ ２の焼結体の結晶構造は殆ん
ど金属的性質を有するα相である。次に、これを９００
℃以下で数１０〜２００時間加熱し半導体的・性質を有
するβ相に変態させ、これに電極端子をつけて熱電気変
換素子としている。Sinter. (FeCo)Si2 made in this way
The crystal structure of the sintered body of (FeMn)S i 2 is an α phase having almost metallic properties. Next, add this to 900
The material is heated for several tens to 200 hours at temperatures below .degree. C. to transform it into a beta phase with semiconducting properties, and electrode terminals are attached to this to form a thermoelectric conversion element.
以上の様な方法でつくられた熱電気変換素子の相対密度
は９９多以上にあげることは難しい。そのため１両半導
体の接合面の機械的強度が弱く。It is difficult to increase the relative density of thermoelectric conversion elements manufactured by the above method to 99% or higher. Therefore, the mechanical strength of the bonding surface between the two semiconductors is weak.
熱発電特性を劣化させると云う欠点があった。It has the disadvantage of deteriorating thermoelectric power generation characteristics.
本発明はこれらの欠点を除去するために、がうス管に封
入された両生導体粉末素材に、最新の高温高圧加工装置
（以下ＨＩＰ装置と略称する）を用いて、高温高圧下で
焼結成型加工を行うことにより、熱電気変換素子の製造
工程の簡略化を計るとともに、その発電特性をあげるこ
とを目的としている。In order to eliminate these drawbacks, the present invention uses the latest high-temperature, high-pressure processing equipment (hereinafter referred to as HIP equipment) to sinter the amphiphilic conductor powder material sealed in the gas tube under high temperature and high pressure. By performing mold processing, the aim is to simplify the manufacturing process of thermoelectric conversion elements and to improve their power generation characteristics.
本発明によれば、ガラス管の中に真空封入されたＮ型半
導体粉末およびＰ型半導体粉末を高温高圧下で焼結成型
する工程を含むことを特徴とする熱電気変換素子の製造
方法が得られる。According to the present invention, there is provided a method for manufacturing a thermoelectric conversion element, which includes a step of sintering N-type semiconductor powder and P-type semiconductor powder vacuum-sealed in a glass tube under high temperature and high pressure. It will be done.
本発明の製造方法の詳細を以下に述べる。 The details of the manufacturing method of the present invention will be described below.
製造しようとする半導体対の粉末素材の焼結温度に合せ
て、適当な軟化温度を有するガラス管をＹ字型に加工し
、その両端を閉管する。そのガラス管の両枝の中にＮ型
およびＰ型半導体の粉末をそれぞれ下部より入れ排気し
、真空封入する。これをガラス管の軟化温度よシ高温で
加熱すると゛封入管パは軟化し、大気圧のだめにガラス
と素材粉末が密着し間隙がなくなる。この状態で数時間
非酸化性のアルゴン、窒素、ヘリウム等の気体でもって
１等方的に加圧すると素材粉末の相対密度ば９９９チ以
上になる。また、ガラス管の形状が保持されたまま焼結
成型される。A glass tube having an appropriate softening temperature is processed into a Y-shape according to the sintering temperature of the powder material of the semiconductor pair to be manufactured, and both ends of the tube are closed. N-type and P-type semiconductor powders are placed into both branches of the glass tube from the bottom, evacuated, and sealed in a vacuum. When this is heated to a temperature higher than the softening temperature of the glass tube, the encapsulated tube becomes soft and the glass and material powder come into close contact with each other due to the atmospheric pressure, eliminating any gaps. If this state is isotropically pressurized with non-oxidizing gas such as argon, nitrogen, helium, etc. for several hours, the relative density of the raw material powder becomes 999 cm or more. Further, the glass tube is sintered and molded while maintaining its shape.
真空封入の際に電接板を装入し、焼結成型後。An electric contact plate is inserted during vacuum sealing, and after the sintering mold is formed.
電極端子とリード線とを２半田付け（又は銀ロー付け）
出来る様にすることも可能である。2. Solder (or silver braze) the electrode terminal and lead wire.
It is also possible to make it possible.
次に第１図及び第２図を参照して本発明の一実施例を説
明する。Next, one embodiment of the present invention will be described with reference to FIGS. 1 and 2.
第１図は、ガ゛ラス管２をＹ字型に加工し両枝に電極端
子１を封入した状態を示している。第２図は、第１図に
示された７字型ガラス管の下端よりＮ型およびＰ型半導
体粉末３および４を両枝に入れ、真空ポンプで排気した
後、密閉する。この状態で上述のＨＩＰ処理を施す。そ
の後７００〜９００℃の温度領域で数１０〜２００時間
熱処理を施し１焼結半導体対を作製しこれを熱電気変換
素子とする。FIG. 1 shows a state in which a glass tube 2 is processed into a Y-shape and electrode terminals 1 are enclosed in both branches. In FIG. 2, N-type and P-type semiconductor powders 3 and 4 are introduced into both branches from the lower end of the 7-shaped glass tube shown in FIG. 1, evacuated with a vacuum pump, and then sealed. In this state, the above-mentioned HIP process is performed. Thereafter, heat treatment is performed in a temperature range of 700 to 900° C. for several tens to 200 hours to produce one sintered semiconductor pair, which is used as a thermoelectric conversion element.
Ｍｎ粉末を含むＦ ｅ Ｓ ｉ ２粉末とＣｏ粉末を含
むＦｅＳ＋２粉末とをＹ字型・ぐイレックスガラス管（
軟化温度約８００℃）の下端より、その両枝に入れ、そ
して真空封入する。この封入管をＨＩＰ装置の中で１０
Ｏｆ）Ｃ”！で加熱しその後アルゴンガスで２０００気
圧、約３時間加圧する。これを更に８２０℃で２０時間
熱処理するとガラス管の形状を保持したままのＵ字型の
焼結半導体対が得られる。封入端に、封着合金５２％Ｎ
ｉＦｅを封着することによって電極としだ。F e S i 2 powder containing Mn powder and FeS+2 powder containing Co powder were placed in a Y-shaped Gyrex glass tube (
It is placed into both branches from the lower end (with a softening temperature of about 800°C), and then vacuum sealed. Place this encapsulation tube in the HIP device for 10 minutes.
Of) C"! and then pressurized with argon gas at 2000 atm for about 3 hours. When this is further heat-treated at 820°C for 20 hours, a U-shaped sintered semiconductor pair that retains the shape of the glass tube is obtained. Sealing alloy 52% N at the end of the seal.
By sealing iFe, it becomes an electrode.
得られた熱電気変換素子に８００℃の温度差を与え、そ
の熱起電力と最大出力とを測定した。その結果を第１表
に示す。比較のために従来の方法で製造された試料につ
いての結果をも第１表に併せ示す。ただし、熱電気変換
素子直径Ｄ ＝ １．６ ｍｍ 。A temperature difference of 800° C. was applied to the obtained thermoelectric conversion element, and its thermoelectromotive force and maximum output were measured. The results are shown in Table 1. For comparison, Table 1 also shows the results for samples manufactured by the conventional method. However, the thermoelectric conversion element diameter D = 1.6 mm.
素子の長さし＝２５門である。The length of the element is 25 gates.
以下今日
第１表 本発明素子の熱発電特性と従来素子のそれとの
比較
〔発明の効果〕
以上説明したように本発明では１例えば、Ｙ字型に加工
されたガラス管の両枝にＮ型およびＰ型半導体の粉末を
下端よりそれぞれ挿入し、真空封入する。この封入管を
高温高圧下で、 ＨＩＰ処理を施すことによって、その
内部の半導体粉末はガラス管の形状が保持されたまま焼
、結成型される。この様にして製造された熱電気変換素
子の相対密度は９９９％以上となり接合面のもろさも補
強されろ。またその発電１１寺性もあがる。Below is Table 1: Comparison of the thermoelectric power generation characteristics of the device of the present invention and those of the conventional device [Effects of the invention] As explained above, in the present invention, 1. For example, the N-type and P-type semiconductor powder are inserted from the lower end and vacuum sealed. By subjecting this sealed tube to HIP treatment under high temperature and high pressure, the semiconductor powder inside the tube is sintered and molded while maintaining the shape of the glass tube. The relative density of the thermoelectric conversion element manufactured in this manner is 999% or more, and the brittleness of the joint surface is also reinforced. In addition, the power generation capacity will also increase.
第１図及び第２図はそれぞれ本発明の一実施例による熱
電気変換素子の製造方法を説明するための断面図である
。
１・・・電極端子、２・・・ガラス管、３・・・Ｎ型半
導体粉末、４・・・Ｐ型半導体粉末。
１２（ｉＵ
第１図 第２図FIGS. 1 and 2 are cross-sectional views for explaining a method of manufacturing a thermoelectric conversion element according to an embodiment of the present invention, respectively. DESCRIPTION OF SYMBOLS 1... Electrode terminal, 2... Glass tube, 3... N-type semiconductor powder, 4... P-type semiconductor powder. 12 (iU Figure 1 Figure 2
Claims (1)
びＰ型半導体粉末を高温高圧下で焼結成型する工程を含
むことを特徴とする熱電気変換素子の製造方法。1. A method for manufacturing a thermoelectric conversion element, which comprises the step of sintering N-type semiconductor powder and P-type semiconductor powder vacuum-sealed in a glass tube under high temperature and high pressure.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59186416A JPH0652809B2 (en) | 1984-09-07 | 1984-09-07 | Method for manufacturing thermoelectric conversion element |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59186416A JPH0652809B2 (en) | 1984-09-07 | 1984-09-07 | Method for manufacturing thermoelectric conversion element |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6165487A true JPS6165487A (en) | 1986-04-04 |
| JPH0652809B2 JPH0652809B2 (en) | 1994-07-06 |
Family
ID=16188037
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59186416A Expired - Lifetime JPH0652809B2 (en) | 1984-09-07 | 1984-09-07 | Method for manufacturing thermoelectric conversion element |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0652809B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01106478A (en) * | 1987-10-19 | 1989-04-24 | Mitsui Mining & Smelting Co Ltd | Manufacture of thermoelectric material |
| EP0455051A2 (en) * | 1990-04-20 | 1991-11-06 | Matsushita Electric Industrial Co., Ltd. | Thermoelectric semiconductor having a porous structure deaerated into a vacuum and thermoelectric panel |
| DE102011084442A1 (en) * | 2011-10-13 | 2013-05-08 | Schott Ag | Thermoelectric component for converting e.g. engine heat energy into current for electronic unit in car, has pair of n-conductors and p-conductors covered by glass tube that exhibits triangular, square or hexagonal cross-section geometry |
-
1984
- 1984-09-07 JP JP59186416A patent/JPH0652809B2/en not_active Expired - Lifetime
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01106478A (en) * | 1987-10-19 | 1989-04-24 | Mitsui Mining & Smelting Co Ltd | Manufacture of thermoelectric material |
| EP0455051A2 (en) * | 1990-04-20 | 1991-11-06 | Matsushita Electric Industrial Co., Ltd. | Thermoelectric semiconductor having a porous structure deaerated into a vacuum and thermoelectric panel |
| USRE35441E (en) * | 1990-04-20 | 1997-02-04 | Matsushita Electrical Industrial Co., Ltd. | Thermoelectric semiconductor having a porous structure deaerated in a vacuum and thermoelectric panel using p-type and n-type thermoelectric semiconductors |
| DE102011084442A1 (en) * | 2011-10-13 | 2013-05-08 | Schott Ag | Thermoelectric component for converting e.g. engine heat energy into current for electronic unit in car, has pair of n-conductors and p-conductors covered by glass tube that exhibits triangular, square or hexagonal cross-section geometry |
| DE102011084442B4 (en) * | 2011-10-13 | 2018-05-03 | Schott Ag | Thermoelectric component with glass coated n- and p-conductors |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0652809B2 (en) | 1994-07-06 |
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