JPH1197210A - Semiconductor with positive resistance temperature coefficient - Google Patents
Semiconductor with positive resistance temperature coefficientInfo
- Publication number
- JPH1197210A JPH1197210A JP9255301A JP25530197A JPH1197210A JP H1197210 A JPH1197210 A JP H1197210A JP 9255301 A JP9255301 A JP 9255301A JP 25530197 A JP25530197 A JP 25530197A JP H1197210 A JPH1197210 A JP H1197210A
- Authority
- JP
- Japan
- Prior art keywords
- alloy
- semiconductor
- curie point
- resistance
- ratio
- 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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- Compositions Of Oxide Ceramics (AREA)
- Thermistors And Varistors (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、正の抵抗温度特性
を有する半導体に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a semiconductor having a positive resistance temperature characteristic.
【０００２】[0002]
【従来の技術】従来より、定温発熱ヒータや、カラーテ
レビの消磁用部品、あるいは過電流保護などに使用され
る素子には、正の抵抗温度特性（以下、ＰＴＣ特性とす
る）を有する半導体が用いられており、特に、抵抗変化
温度（以下、キュリー点とする）以上になると急激に高
抵抗化するというＰＴＣ特性を有するＢａＴｉＯ3系の
半導体セラミックが広く用いられている。2. Description of the Related Art Conventionally, semiconductors having positive resistance temperature characteristics (hereinafter, referred to as PTC characteristics) have been used for devices used for constant temperature heating heaters, degaussing parts for color televisions, or overcurrent protection. In particular, BaTiO 3 -based semiconductor ceramics having PTC characteristics in which the resistance rapidly increases when the temperature exceeds a resistance change temperature (hereinafter referred to as the Curie point) are widely used.
【０００３】このような用途に使用されるＰＴＣ特性を
有する半導体セラミックには、特に、その抵抗値がある
特定温度でなるべく急激に上昇することが望まれてお
り、この課題に対応するものとしてＢａＴｉＯ3中にＭ
ｎを添加して抵抗値の上昇率を高めた半導体セラミック
などが実施されていた。[0003] It is desired that the semiconductor ceramic having PTC characteristics used for such an application has a resistance value which rises as rapidly as possible at a specific temperature as much as possible. M in 3
Semiconductor ceramics and the like in which the rate of increase in the resistance value is increased by adding n have been implemented.
【０００４】一方、従来のＢａＴｉＯ3中にＭｎを添加
した半導体セラミックとは別に、「日本セラミックス協
会１９９２年会（題目：Ｂｉ4Ｔｉ3Ｏ12系セラミックス
の半導体化及び比抵抗温度特性）」（鄒・岡田・本間、
日本セラミックス協会、１９９２）にあるように、抵抗
変化比が高いＢｉ−Ｔｉ−Ｏ系の半導体セラミックが提
案されている。On the other hand, apart from the semiconductor ceramic obtained by adding Mn in the conventional BaTiO 3, "Ceramic Society of Japan 1992 Annual (Title: semiconductive and specific resistance-temperature characteristic of a Bi 4 Ti 3 O 12 ceramics)" ( Zou, Okada, Honma,
As described in the Ceramic Society of Japan, 1992), a Bi-Ti-O-based semiconductor ceramic having a high resistance change ratio has been proposed.
【０００５】[0005]
【発明が解決しようとする課題】しかしながら、近年、
進歩を続ける電子機器に十分に満足するように、ＰＴＣ
特性を有する半導体に対してＰＴＣ特性のさらなる改善
が求められている。However, in recent years,
To fully satisfy the evolving electronic equipment, PTC
Further improvement of PTC characteristics is required for semiconductors having characteristics.
【０００６】このような状況において、従来のＢｉ−Ｔ
ｉ−Ｏ系の半導体セラミックは、抵抗変化比が高いもの
の、キュリー点が２７０℃付近と高いため、半導体セラ
ミック素子の電極やケースなどを高い温度にまで耐えら
れるようにしておく必要があるという問題があった。In such a situation, the conventional Bi-T
Although the i-O-based semiconductor ceramic has a high resistance change ratio, its Curie point is as high as about 270 ° C., so that it is necessary to make the electrodes and the case of the semiconductor ceramic element withstand high temperatures. was there.
【０００７】本発明は、キュリー点前後の抵抗変化比が
従来のＢｉ−Ｔｉ−Ｏ系の半導体セラミックの水準を維
持しており、かつ、キュリー点がＢｉ−Ｔｉ−Ｏ系の半
導体セラミックのもの（約２７０℃）より低いＰＴＣ特
性を有する半導体を提供することにある。According to the present invention, the resistance change ratio before and after the Curie point is maintained at the level of a conventional Bi-Ti-O based semiconductor ceramic, and the Curie point is a Bi-Ti-O based semiconductor ceramic. It is to provide a semiconductor having a lower PTC characteristic (about 270 ° C.).
【０００８】[0008]
【課題を解決するための手段】第１の発明のＰＴＣ特性
を有する半導体は、比抵抗１kΩ・cm以上の材料を主成
分とし、前記材料中に、副成分としてＢｉ−Ｓｎ合金を
分散させてなることを特徴とする。According to the first aspect of the present invention, there is provided a semiconductor having PTC characteristics comprising a material having a specific resistance of 1 kΩ · cm or more as a main component, and a Bi—Sn alloy dispersed as a subcomponent in the material. It is characterized by becoming.
【０００９】このような組成にすることによって、キュ
リー点前後の抵抗変化比をＢｉ−Ｔｉ−Ｏ系の半導体の
もの程度とするとともに、キュリー点を２７０℃以下と
することができる。By adopting such a composition, the resistance change ratio before and after the Curie point can be set to about that of a Bi-Ti-O-based semiconductor, and the Curie point can be set to 270 ° C. or lower.
【００１０】また、第２の発明の半導体材料において
は、ＢｉとＳｎとの組成比Ｓｎ／Ｂｉ（原子比）が０．
3〜０．８の範囲であることが好ましい。Further, in the semiconductor material of the second invention, the composition ratio of Bi to Sn, Sn / Bi (atomic ratio) is 0.1.
It is preferably in the range of 3 to 0.8.
【００１１】ＢｉとＳｎとをこのような組成比にするこ
とによって、キュリー点を２0０℃以下とより低くし、
半導体素子の信頼性を高めることができる。また、キュ
リー点前後の抵抗変化比を２０００以上とより高くする
ことができる。By setting Bi and Sn in such a composition ratio, the Curie point is lowered to 200 ° C. or less,
The reliability of the semiconductor element can be improved. Further, the resistance change ratio before and after the Curie point can be increased to 2000 or more.
【００１２】[0012]
【発明の実施の形態】本発明のＰＴＣ特性を有する半導
体の主成分として用いられる材料は、好ましいものとし
て、Ｔｉ−Ｎｂ−Ｏ系、Ｂａ−Ｔｉ−Ｎｂ−Ｏ系、Ｂｉ
−Ｔｉ−Ｎｂ−Ｏ系等が挙げられるが、特にこれらに限
定するものではなく、比抵抗が１ｋΩ・cm以上であれ
ば、アルミナやジルコニアなどのセラミックでもよい
し、この他ガラスなどの無機材料でもよい。また、エポ
キシ樹脂やフェノール樹脂等の熱硬化性樹脂、ポリイミ
ドやポリアミド等の熱可塑性樹脂等の有機材料も用いる
ことができる。BEST MODE FOR CARRYING OUT THE INVENTION The material used as the main component of the semiconductor having PTC characteristics of the present invention is preferably a Ti-Nb-O-based material, a Ba-Ti-Nb-O-based material, or a Bi-based material.
-Ti-Nb-O type, etc., but not particularly limited thereto. Ceramics such as alumina and zirconia may be used as long as the specific resistance is 1 kΩ · cm or more, and other inorganic materials such as glass. May be. Further, an organic material such as a thermosetting resin such as an epoxy resin or a phenol resin, or a thermoplastic resin such as polyimide or polyamide can also be used.
【００１３】また、上記材料中に分散しているＢｉ−Ｓ
ｎ合金の分散状態は、特に数値的に限定するものではな
いが、できるだけ一様に分散している状態であることが
好ましい。また、上記Ｂｉ−Ｓｎ合金の平均粒径は、大
きすぎるとＰＴＣ特性が低下し、小さすぎると酸化され
て高抵抗化するという理由から、０．１μｍ〜１００μ
ｍであることが好ましい。また、上記Ｂｉ−Ｓｎ合金の
添加量は、多すぎるとＰＴＣ特性が低下し、少なすぎる
と高抵抗化するという理由から、上記材料１００重量部
に対して、５０重量部〜１５０重量部であることが好ま
しい。Further, Bi-S dispersed in the above material
The dispersion state of the n-alloy is not particularly limited numerically, but it is preferable that the dispersion state is as uniform as possible. Further, the average particle size of the Bi—Sn alloy is 0.1 μm to 100 μm because the PTC characteristics are deteriorated if too large, and if the average particle size is too small, it is oxidized to increase the resistance.
m is preferable. Further, the addition amount of the Bi-Sn alloy is 50 parts by weight to 150 parts by weight with respect to 100 parts by weight of the material, because if the amount is too large, the PTC property is reduced, and if the amount is too small, the resistance increases. Is preferred.
【００１４】次に、本発明を実施例に基づき、さらに詳
しく説明するが、本発明はかかる実施例のみに限定され
るものではない。Next, the present invention will be described in more detail based on examples, but the present invention is not limited to only these examples.
【００１５】[0015]
【実施例】本発明の半導体材料を以下のように作製し
た。まず、主成分となる材料として、（Ｔｉ1-xＮｂx）
Ｏ2（０≦ｘ≦０．００１）を用意した。なお、材料
（Ｔｉ1-xＮｂx）Ｏ2は、ｘの値を変動させることによ
って、比抵抗を変動させることができる。この材料に、
副成分として、平均粒径を２０μｍとしたＳｎ−Ｂｉ合
金粉末を重量比で１：１の割合となるように調合した
後、ＰＳＺボールとともに５時間水中で粉砕混合し、混
合粉を得た。EXAMPLE A semiconductor material of the present invention was produced as follows. First, (Ti 1-x Nb x )
O 2 (0 ≦ x ≦ 0.001) was prepared. The specific resistance of the material (Ti 1-x Nb x ) O 2 can be changed by changing the value of x. In this material,
As an auxiliary component, a Sn-Bi alloy powder having an average particle diameter of 20 µm was prepared so as to have a weight ratio of 1: 1 and then pulverized and mixed with water with PSZ balls for 5 hours to obtain a mixed powder.
【００１６】得られた混合粉にバインダーを混合し、１
２ｍｍφ×１ｍｍｔに乾式プレス成形して成形体とし、
この成形体をＨ2／Ｎ2雰囲気中において１３００℃で還
元焼成し、焼結体を得た。[0016] A binder is mixed with the obtained mixed powder,
Dry press molding to 2mmφ x 1mmt to form a molded body,
This compact was reduced and fired at 1300 ° C. in an H 2 / N 2 atmosphere to obtain a sintered body.
【００１７】このとき、Ｂｉ−Ｓｎ比の原子比と、（Ｔ
ｉ1-xＮｂx）Ｏ2の単独の比抵抗とを変動させて各試料
とし、キュリー点と、キュリー点の前後５０℃での抵抗
比である抵抗変化比とを測定し、その結果を表１に示し
た。なお、表中の※印は本発明の範囲外であることを示
す。また、表中の評価欄の○印は良好、△印は実用上差
し支えなし、×印は実用上問題有りであることをそれぞ
れ示す。At this time, the atomic ratio of the Bi—Sn ratio and (T
The specific resistance of i 1-x Nb x ) O 2 was varied to make each sample, and the Curie point and the resistance change ratio, which is the resistance ratio at 50 ° C. before and after the Curie point, were measured. The results are shown in Table 1. Note that the asterisks in the table indicate that they are outside the scope of the present invention. Further, in the evaluation column in the table, a circle indicates good, a triangle indicates no problem in practical use, and a cross indicates that there is a problem in practical use.
【００１８】[0018]
【表１】 [Table 1]
【００１９】表１に示すように、比抵抗１ｋΩ・cm以上
の材料中にＢｉ−Ｓｎ合金を添加した半導体は、キュリ
ー点が低く、かつ、抵抗変化比が高いことが確認でき
る。As shown in Table 1, it can be confirmed that a semiconductor obtained by adding a Bi—Sn alloy to a material having a specific resistance of 1 kΩ · cm or more has a low Curie point and a high resistance change ratio.
【００２０】ここで、本発明のＰＴＣ特性を有する半導
体において、主成分となる材料の比抵抗を１ｋΩ・cm以
上としたのは、試料番号９のように、材料の比抵抗が１
ｋΩ・cmより小さい場合には、材料の抵抗変化比Ｒ高温
／Ｒ低温が１０００より小さくなり、好ましくないから
である。Here, in the semiconductor having the PTC characteristic of the present invention, the specific resistance of the material as a main component was set to 1 kΩ · cm or more, as shown in Sample No. 9, when the specific resistance of the material was 1 kΩ · cm.
If it is smaller than kΩ · cm, the resistance change ratio R high / low temperature of the material becomes smaller than 1000, which is not preferable.
【００２１】また、Ｓｎ−Ｂｉ合金のＳｎ、Ｂｉの組成
比Ｓｎ／Ｂｉを０．３〜０．８の範囲に限定したのは、
試料番号１のように、Ｓｎ／Ｂｉが０．１より小さい場
合には、抵抗上昇温度が２００℃を越えてしまい、好ま
しくないからである。The reason why the Sn / Bi composition ratio Sn / Bi of the Sn—Bi alloy is limited to the range of 0.3 to 0.8 is as follows.
This is because when Sn / Bi is smaller than 0.1 as in Sample No. 1, the resistance rise temperature exceeds 200 ° C., which is not preferable.
【００２２】また、試料番号６のように、Ｓｎ／Ｂｉが
０．８より大きい場合には、抵抗変化比Ｒ高温／Ｒ低温
が２０００より小さくなり、好ましくないからである。Further, when Sn / Bi is larger than 0.8 as in sample No. 6, the resistance change ratio R high / low temperature becomes smaller than 2000, which is not preferable.
【００２３】（実施例２）主成分となる材料としてＡｌ
2Ｏ3粉末を用意し、実施例１と同様にして成形体を得
た。そして、得られた成形体をＨ2／Ｎ2雰囲気中におい
て１４００℃で還元焼成し、焼結体を得た。(Example 2) Al as a main component material
2 O 3 powder was prepared, and a molded body was obtained in the same manner as in Example 1. Then, the obtained molded body was reduced and fired at 1400 ° C. in an H 2 / N 2 atmosphere to obtain a sintered body.
【００２４】このとき、Ａｌ2Ｏ3単独の比抵抗を１．２
×１０11Ω・cm、Ｂｉ／Ｓｎ＝０．５に固定して実施例
１と同じく特性評価を行った。それぞれの値は、キュリ
ー点が１５０℃、抵抗変化比が３２００となり、本発明
の課題を解決するにあたり、十分な特性値であることを
確認した。At this time, the specific resistance of Al 2 O 3 alone is set to 1.2
The characteristics were evaluated in the same manner as in Example 1 while fixing at × 10 11 Ω · cm and Bi / Sn = 0.5. Each value was found to have a Curie point of 150 ° C. and a resistance change ratio of 3200, which were sufficient characteristic values to solve the problem of the present invention.
【００２５】[0025]
【発明の効果】本発明の正の抵抗温度特性を有する半導
体は、比抵抗１ｋΩ・cm以上の材料を主成分とし、その
材料中に、副成分としてＢｉ−Ｓｎ合金を分散させてい
るので、キュリー点前後の抵抗変化比が従来のＢｉ−Ｔ
ｉ−Ｏ系の半導体セラミックの水準を維持しており、か
つ、キュリー点がＢｉ−Ｔｉ−Ｏ系の半導体セラミック
のもの（約２７０℃）より低いＰＴＣ特性を有する半導
体とすることができる。The semiconductor having a positive temperature coefficient of resistance according to the present invention comprises a material having a specific resistance of 1 kΩ · cm or more as a main component and a Bi—Sn alloy as a subcomponent dispersed in the material. The resistance change ratio before and after the Curie point is
A semiconductor which maintains the level of an i-O-based semiconductor ceramic and has a PTC characteristic whose Curie point is lower than that of a Bi-Ti-O-based semiconductor ceramic (about 270 ° C) can be obtained.
Claims (2)
し、前記材料中に、副成分としてＢｉ−Ｓｎ合金を分散
させてなることを特徴とする正の抵抗温度特性を有する
半導体。1. A semiconductor having a positive resistance-temperature characteristic, comprising a material having a specific resistance of 1 kΩ · cm or more as a main component, and a Bi—Sn alloy dispersed as a subcomponent in the material.
Ｓｎとの組成比Ｓｎ／Ｂｉ（原子比）が０．３〜０．８
の範囲であることを特徴とする請求項１に記載の正の抵
抗温度特性を有する半導体。2. The composition ratio of Bi to Sn contained in the Bi—Sn alloy, Sn / Bi (atomic ratio), is 0.3 to 0.8.
2. The semiconductor having a positive resistance-temperature characteristic according to claim 1, wherein:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25530197A JP3829431B2 (en) | 1997-09-19 | 1997-09-19 | Semiconductor ceramic with positive resistance temperature characteristics |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25530197A JP3829431B2 (en) | 1997-09-19 | 1997-09-19 | Semiconductor ceramic with positive resistance temperature characteristics |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH1197210A true JPH1197210A (en) | 1999-04-09 |
| JP3829431B2 JP3829431B2 (en) | 2006-10-04 |
Family
ID=17276883
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP25530197A Expired - Fee Related JP3829431B2 (en) | 1997-09-19 | 1997-09-19 | Semiconductor ceramic with positive resistance temperature characteristics |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3829431B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016136321A1 (en) * | 2015-02-25 | 2016-09-01 | 株式会社村田製作所 | Composite material and manufacturing method thereof |
-
1997
- 1997-09-19 JP JP25530197A patent/JP3829431B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016136321A1 (en) * | 2015-02-25 | 2016-09-01 | 株式会社村田製作所 | Composite material and manufacturing method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3829431B2 (en) | 2006-10-04 |
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