JPH04104951A - Barium titanate-based semiconductive porcelain material - Google Patents
Barium titanate-based semiconductive porcelain materialInfo
- Publication number
- JPH04104951A JPH04104951A JP2219528A JP21952890A JPH04104951A JP H04104951 A JPH04104951 A JP H04104951A JP 2219528 A JP2219528 A JP 2219528A JP 21952890 A JP21952890 A JP 21952890A JP H04104951 A JPH04104951 A JP H04104951A
- Authority
- JP
- Japan
- Prior art keywords
- mol
- semiconductor
- barium titanate
- manganese
- specific resistance
- 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.)
- Pending
Links
- 229910002113 barium titanate Inorganic materials 0.000 title claims abstract description 15
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 title claims description 13
- 229910052573 porcelain Inorganic materials 0.000 title abstract description 10
- 239000000463 material Substances 0.000 title abstract description 7
- 239000011572 manganese Substances 0.000 claims abstract description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 5
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 4
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 4
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 4
- 229910052776 Thorium Inorganic materials 0.000 claims abstract description 3
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 3
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 3
- 239000004065 semiconductor Substances 0.000 claims description 21
- 229910010293 ceramic material Inorganic materials 0.000 claims description 8
- 229910003781 PbTiO3 Inorganic materials 0.000 abstract description 3
- 229910052715 tantalum Inorganic materials 0.000 abstract description 3
- 229910002971 CaTiO3 Inorganic materials 0.000 abstract 2
- 229910002370 SrTiO3 Inorganic materials 0.000 abstract 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 abstract 2
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 8
- 239000000203 mixture Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910000807 Ga alloy Inorganic materials 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
この発明はチタン酸バリウム系半導体磁器材料に関する
。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) This invention relates to barium titanate-based semiconductor ceramic materials.
（従来技術）
チタン酸バリウム系半導体磁器に用いられる材料は、チ
タン酸バリウムを主成分とし、半導体化剤となるＹ、Ｌ
ａ、Ｃｅなどの希土類元素、ＮｂＢ ｉ、Ｓｂ、Ｗ、Ｔ
ｈ、Ｔａなどの中から選ばれる少なくとも１種類を添加
含有させたものである。このような材料を用いた半導体
磁器は、常温において小さい比抵抗を有し、キュリー点
を趙えると著しい正の抵抗温度変化を示すという特徴を
有している。通常、チタン酸バリウム系半導体磁器では
、その主成分であるチタン酸バリウムの影響により、そ
のキュリー点が１２０℃付近にある。(Prior art) The material used for barium titanate-based semiconductor porcelain has barium titanate as its main component, and Y and L as semiconductor agents.
a, rare earth elements such as Ce, NbBi, Sb, W, T
At least one selected from among h, Ta, etc. is added and contained. Semiconductor porcelain made of such materials has a characteristic that it has a small resistivity at room temperature and exhibits a significant positive temperature change in resistance when the Curie point is exceeded. Normally, barium titanate-based semiconductor porcelain has a Curie point around 120° C. due to the influence of its main component, barium titanate.
このキュリー点を高温側に移行させるために、Ｂａの一
部をｐｂで置換することが知られている。In order to shift this Curie point to the high temperature side, it is known to replace a part of Ba with Pb.
逆に、キュリー点を低温側に移行させるために、Ｂａの
一部をＳｒで置換したり、Ｔｉの一部をＺｒ、Ｓｎなど
で置換することが知られている。On the other hand, in order to shift the Curie point to a lower temperature side, it is known to replace a portion of Ba with Sr or a portion of Ti with Zr, Sn, or the like.
また、チタン酸バリウム系半導体材料にマンガンをＭｎ
に換算して０．０３〜０．１５モル％添加することによ
り、キュリー点を超えたのちの抵抗温度変化率を著しく
増大させることが知られている。さらに、ＳｉＯ□を０
．５〜５モル％添加することにより、常温における比抵
抗を小さくするとともに安定したものにすることが知ら
れている。In addition, manganese is added to barium titanate-based semiconductor materials.
It is known that adding 0.03 to 0.15 mol % (calculated as 0.03 to 0.15 mol %) significantly increases the resistance temperature change rate after the Curie point has been exceeded. Furthermore, SiO□ is 0
．． It is known that by adding 5 to 5 mol %, the specific resistance at room temperature can be reduced and stabilized.
（発明が解決しようとする課題）
このようなチタン酸バリウム系半導体磁器材料を用いた
半導体磁器の耐電圧特性を上げるため、Ｂａの一部をＣ
ａまたはＣａ、Ｓｒで置換し、Ｍｎ、ＳｉＯ□を添加し
たものが提案されている。(Problem to be Solved by the Invention) In order to improve the withstand voltage characteristics of semiconductor porcelain using such barium titanate-based semiconductor porcelain material, a part of Ba is replaced with C.
Substitution with a, Ca, and Sr and addition of Mn and SiO□ have been proposed.
しかし、比抵抗が１０Ω■以下のものでは、絶縁破壊電
圧が最高のもので４８Ｖ／ｍの値しか示さず、実用上十
分な値ではない。However, when the specific resistance is 10 Ω or less, the maximum dielectric breakdown voltage is only 48 V/m, which is not a practically sufficient value.
また、Ｂａの一部をＰｂ、Ｓｒ、Ｃａで同時に置換した
ものでは、優れた耐電圧特性を得ることができると報告
されているが、Ｍｎ添加量が０゜０３モル％以上でかつ
半導体化剤が０．２モル％より多かったため、３５Ω■
までしか比抵抗を下げることができなかった。Furthermore, it has been reported that excellent withstand voltage characteristics can be obtained by replacing a part of Ba with Pb, Sr, and Ca at the same time, but if the amount of Mn added is 0.03 mol% or more and Since the amount of the agent was more than 0.2 mol%, the resistance was 35Ω■
It was possible to lower the resistivity only up to
それゆえに、この発明の主たる目的は、常温における比
抵抗が小さく、かつ耐電圧が高い半導体磁器を得ること
ができるチタン酸バリウム系半導体磁器材料を提供する
ことである。Therefore, the main object of the present invention is to provide a barium titanate-based semiconductor ceramic material that can yield a semiconductor ceramic material that has a low specific resistance at room temperature and a high withstand voltage.
（課題を解決するための手段）
この発明は、ＢａＴｉ０．が３０〜９５モル％Ｃａ Ｔ
ｉ Ｏｓが３〜２５モル％、５ｒＴｉ○３が１〜２５
モル％、 Ｐ ｂ Ｔ ｉ Ｏ３が１〜３０モル％か
らなる主成分に対して、マンガンをＭｎに換算して０．
０３モル％以上０．１モル％未満、シリカをＳｉＯ□に
換算して０．５〜５モル％、および半導体化剤として、
Ｎｂ、Ｂｉ、Ｓｂ、Ｗ。(Means for Solving the Problems) This invention provides BaTi0. is 30-95 mol% CaT
iOs is 3-25 mol%, 5rTi○3 is 1-25
With respect to the main component consisting of 1 to 30 mol% of PbT i O3, manganese is 0.0% in terms of Mn.
03 mol% or more and less than 0.1 mol%, 0.5 to 5 mol% in terms of silica as SiO□, and as a semiconducting agent,
Nb, Bi, Sb, W.
Ｔｈ、Ｔａおよび希土類元素の中から選ばれる少なくと
も１種類を０．０５〜０．２モル％添加含有した、チタ
ン酸バリウム系半導体磁器材料である。This is a barium titanate-based semiconductor ceramic material containing 0.05 to 0.2 mol% of at least one selected from Th, Ta, and rare earth elements.
（作用）
主成分が、ＢａＴｉ０．、ＣａＴｉ０．．５ｒＴｉ０３
．ＰｂＴｉＯ３からなり、言い換えれば、ＢａＴｉ○、
のＢａの一部をＣａ、Ｓｒ、ｐｂで同時に置換したもの
である。また、マンガンをＭｎに換算して０．０３モル
％以上０．１モル％未満かつ半導体化剤を０．０５〜０
．２モル％添加することにより、比抵抗が１０Ω■以下
で耐電圧が１００Ｖ／鶴以上になる。(Action) The main component is BaTi0. , CaTi0. ．． 5rTi03
．． Consisting of PbTiO3, in other words, BaTi○,
Part of Ba is replaced with Ca, Sr, and pb at the same time. In addition, manganese is 0.03 mol% or more and less than 0.1 mol% in terms of Mn, and the semiconducting agent is 0.05 to 0.
．． By adding 2 mol%, the specific resistance becomes 10 Ω or less and the withstand voltage becomes 100 V/Tsuru or more.
（発明の効果）
この発明によれば、比抵抗が小さく、かつ耐電圧の高い
半導体磁器を作製可能なチタン酸バリウム系半導体磁器
材料を得ることができる。(Effects of the Invention) According to the present invention, it is possible to obtain a barium titanate-based semiconductor ceramic material that has a low specific resistance and can produce a semiconductor ceramic that has a high withstand voltage.
この発明の上述の目的、その他の目的、特徴および利点
は、以下の実施例の詳細な説明から一層明らかとなろう
。The above objects, other objects, features and advantages of the present invention will become more apparent from the detailed description of the following embodiments.
（実施例）
まず、原料として、主成分であるＢａＣＯ５゜Ｃａ Ｃ
ｏｇ ＋ Ｓ ｒ ＣＯｓ 、 Ｐ ｂ、０４ 、
Ｔ ｔ ０２、半導体化剤であるＹｚ Ｏｓ ＋ Ｌ
ａｇ Ｏｓ 、Ｃｅ０ｚ 、Ｎｄｚ ０３ 、添加物で
あるＭｎＣＯ５，ＳｉＯ□などを準備した。これらの各
原料を表１に示す比率の半導体磁器材料が得られるよう
に配合し、湿式混合して混合物を得た。この混合物を脱
水乾燥し、１１５０℃で２時間仮焼して仮焼物を得た。(Example) First, as a raw material, the main component BaCO5゜CaC
og + S r COs , P b , 04 ,
T t 02, semiconducting agent Yz Os + L
Ag Os , Ce0z , Ndz 03 , and additives such as MnCO5 and SiO□ were prepared. These raw materials were blended so as to obtain a semiconductor ceramic material having the ratio shown in Table 1, and wet-mixed to obtain a mixture. This mixture was dehydrated and dried, and calcined at 1150° C. for 2 hours to obtain a calcined product.
さらに、この仮焼物を粉砕し、バインダを加えて造粒し
、成形圧力１０００ｋｇ／ａＪで円板状に成形して成形
物を得た。この成形物を１３６０℃で焼成し、直径１７
．５ｍ、厚さ０．６ｍの円板状の半導体磁器を得た。Further, this calcined product was crushed, granulated with the addition of a binder, and molded into a disk shape at a molding pressure of 1000 kg/aJ to obtain a molded product. This molded product was fired at 1360°C, and the diameter was 17.
．． A disk-shaped semiconductor porcelain measuring 5 m long and 0.6 m thick was obtained.
得られた半導体磁器の両生面にＩｎ−Ｇａ合金の電極を
形成し、試料とした。In--Ga alloy electrodes were formed on the amphibatic surfaces of the obtained semiconductor porcelain to prepare a sample.
これらの試料について、常温（２５℃）における比抵抗
、耐電圧特性およびキュリー点を測定して、表２に示し
た。なお、表中＊印を付したものはこの発明の範囲外の
ものであり、それ以外はこの発明の範囲内のものである
。Regarding these samples, the specific resistance, withstand voltage characteristics, and Curie point at room temperature (25° C.) were measured and shown in Table 2. In addition, those marked with * in the table are outside the scope of this invention, and the others are within the scope of this invention.
次に、各組成の限定理由について説明する。Next, the reasons for limiting each composition will be explained.
試料番号２１のように、ＢａＴｉ０．が３θモル％未満
では、比抵抗が大きくなる。一方、試料番号２６のよう
に、ＢａＴｉ０：＋が９５モル％を超えると、耐電圧特
性の改善効果がない。Like sample number 21, BaTi0. is less than 3θ mol %, the specific resistance becomes large. On the other hand, when BaTi0:+ exceeds 95 mol %, as in sample number 26, there is no effect of improving withstand voltage characteristics.
試料番号３．５．６のように、ＣａＴｉ０．が３モル％
未満では、耐電圧特性の改善効果がない。As in sample number 3.5.6, CaTi0. is 3 mol%
If it is less than that, there is no effect of improving withstand voltage characteristics.
一方、試料番号２７のように、ＣａＴｉＯｓが２５モル
％を超えると、比抵抗が大きくなる。On the other hand, when CaTiOs exceeds 25 mol %, as in sample number 27, the specific resistance increases.
試料番号２のように、５ｒＴｉＯ，が１モル％未満では
、耐電圧特性の改善効果がない。一方、試料番号１のよ
うに、５ｒＴｉＯ，が２５モル％を超えると、耐電圧特
性の改善効果がない。As in Sample No. 2, if 5rTiO is less than 1 mol %, there is no effect of improving withstand voltage characteristics. On the other hand, when 5rTiO exceeds 25 mol %, as in Sample No. 1, there is no effect of improving withstand voltage characteristics.
試料番号４のように、ｐｂＴｉｏ２が１モル％未満では
、耐電圧特性の改善効果がない。一方、試料番号２８の
ように、Ｐ ｂ Ｔ ｉ Ｏ，が３０モル％を超えると
、半導体化が困難となる。If pbTio2 is less than 1 mol %, as in sample number 4, there is no effect of improving withstand voltage characteristics. On the other hand, when P b T i O, exceeds 30 mol %, as in sample number 28, it becomes difficult to make it into a semiconductor.
試料番号１３のように、添加物としてのＭｎが０．１モ
ル％以上では、比抵抗を３５Ω１以下にすることができ
ず、小さい比抵抗を得ることができない。一方、試料番
号１４のように、Ｍｎが０．０３モル％未満では、耐電
圧特性の改善効果が少ない。As in Sample No. 13, when Mn as an additive is 0.1 mol% or more, the specific resistance cannot be made 35Ω1 or less, and a small specific resistance cannot be obtained. On the other hand, if the Mn content is less than 0.03 mol %, as in Sample No. 14, the effect of improving withstand voltage characteristics is small.
試料番号１１のように半導体化剤が０．０５モル％未満
となるか、試料番号１２のように半導体化剤が０，２モ
ル％を超えると、比抵抗が大きくなりすぎる。If the amount of the semiconducting agent is less than 0.05 mol % as in Sample No. 11, or more than 0.2 mol % as in Sample No. 12, the specific resistance becomes too large.
試料番号２０のように、Ｓｉｎ、が０．５モル％よりも
少ない場合では、耐電圧特性の改善効果がない。一方、
試料番号１８のように、Ｓｉｎ。When the amount of Sin is less than 0.5 mol %, as in sample number 20, there is no effect of improving withstand voltage characteristics. on the other hand,
Like sample number 18, Sin.
が５モル％を超えると、融着がおこる。If it exceeds 5 mol%, fusion will occur.
それに対して、この発明の範囲内のチタン酸バリウム系
半導体磁器材料を用いれば、１０Ω備以下の小さい比抵
抗を有し、かつ１００Ｖ／ｍ以上の耐電圧を有する半導
体磁器を得ることができる。On the other hand, if a barium titanate-based semiconductor ceramic material within the scope of the present invention is used, it is possible to obtain a semiconductor ceramic having a small resistivity of 10Ω or less and a withstand voltage of 100V/m or more.
特許出願人 株式会社 村田製作所 代理人 弁理士 岡 １） 全 啓Patent applicant Murata Manufacturing Co., Ltd. Agent: Patent Attorney Oka 1) Zenhiro
Claims (1)
が３〜２５モル％，ＳｒＴｉＯ＿３が１〜２５モル％，
ＰｂＴｉＯ＿３が１〜３０モル％からなる主成分に対し
て、 マンガンをＭｎに換算して０．０３モル％以上０．１モ
ル％未満、 シリカをＳｉＯ＿２に換算して０．５〜５モル％、およ
び半導体化剤として、Ｎｂ，Ｂｉ，Ｓｂ，Ｗ，Ｔｈ，Ｔ
ａおよび希土類元素の中から選ばれる少なくとも１種類
を０．０５〜０．２モル％添加含有した、チタン酸バリ
ウム系半導体磁器材料。[Claims] BaTiO_3 is 30 to 95 mol%, CaTiO_3
is 3 to 25 mol%, SrTiO_3 is 1 to 25 mol%,
With respect to the main component consisting of 1 to 30 mol% of PbTiO_3, manganese is 0.03 mol% or more and less than 0.1 mol% in terms of Mn, silica is 0.5 to 5 mol% in terms of SiO_2, and as a semiconductor agent, Nb, Bi, Sb, W, Th, T
A barium titanate-based semiconductor ceramic material containing 0.05 to 0.2 mol% of at least one selected from a and rare earth elements.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2219528A JPH04104951A (en) | 1990-08-20 | 1990-08-20 | Barium titanate-based semiconductive porcelain material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2219528A JPH04104951A (en) | 1990-08-20 | 1990-08-20 | Barium titanate-based semiconductive porcelain material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04104951A true JPH04104951A (en) | 1992-04-07 |
Family
ID=16736895
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2219528A Pending JPH04104951A (en) | 1990-08-20 | 1990-08-20 | Barium titanate-based semiconductive porcelain material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04104951A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998022411A1 (en) * | 1996-11-20 | 1998-05-28 | Murata Manufacturing Co., Ltd. | Barium titanate-base semiconducting ceramic composition |
| WO2011002021A1 (en) * | 2009-07-01 | 2011-01-06 | 株式会社村田製作所 | Semiconductor ceramic and positive-coefficient thermistor |
| EP2774904A4 (en) * | 2011-11-01 | 2016-01-27 | Murata Manufacturing Co | Ptc thermistor and method for manufacturing ptc thermistor |
| CN105622091A (en) * | 2014-11-24 | 2016-06-01 | 三星电机株式会社 | Dielectric ceramic composition and electronic device using the same |
| JP2017014093A (en) * | 2015-07-06 | 2017-01-19 | サムソン エレクトロ−メカニックス カンパニーリミテッド． | Dielectric ceramic composition and multilayer ceramic capacitor containing the same |
-
1990
- 1990-08-20 JP JP2219528A patent/JPH04104951A/en active Pending
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998022411A1 (en) * | 1996-11-20 | 1998-05-28 | Murata Manufacturing Co., Ltd. | Barium titanate-base semiconducting ceramic composition |
| US6187707B1 (en) | 1996-11-20 | 2001-02-13 | Murata Manufacturing Co., Ltd. | Barium titanate-based semiconductive ceramic composition |
| CN1089735C (en) * | 1996-11-20 | 2002-08-28 | 株式会社村田制作所 | Barium titanate-base semiconducting ceramic composition |
| WO2011002021A1 (en) * | 2009-07-01 | 2011-01-06 | 株式会社村田製作所 | Semiconductor ceramic and positive-coefficient thermistor |
| CN102471164A (en) * | 2009-07-01 | 2012-05-23 | 株式会社村田制作所 | Semiconductor ceramic and positive-coefficient thermistor |
| JPWO2011002021A1 (en) * | 2009-07-01 | 2012-12-13 | 株式会社村田製作所 | Semiconductor ceramic and positive temperature coefficient thermistor |
| US8390421B2 (en) | 2009-07-01 | 2013-03-05 | Murata Manufacturing Co., Ltd. | Semiconductor ceramic and positive-coefficient characteristic thermistor |
| JP5510455B2 (en) * | 2009-07-01 | 2014-06-04 | 株式会社村田製作所 | Semiconductor ceramic and positive temperature coefficient thermistor |
| EP2774904A4 (en) * | 2011-11-01 | 2016-01-27 | Murata Manufacturing Co | Ptc thermistor and method for manufacturing ptc thermistor |
| CN105622091A (en) * | 2014-11-24 | 2016-06-01 | 三星电机株式会社 | Dielectric ceramic composition and electronic device using the same |
| JP2017014093A (en) * | 2015-07-06 | 2017-01-19 | サムソン エレクトロ−メカニックス カンパニーリミテッド． | Dielectric ceramic composition and multilayer ceramic capacitor containing the same |
| JP2021004172A (en) * | 2015-07-06 | 2021-01-14 | サムソン エレクトロ−メカニックス カンパニーリミテッド． | Dielectric porcelain composition and multilayer ceramic capacitor containing the same |
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