JPH0529110A - Grain boundary oxidation type voltage nonlinear resistor element - Google Patents
Grain boundary oxidation type voltage nonlinear resistor elementInfo
- Publication number
- JPH0529110A JPH0529110A JP3204934A JP20493491A JPH0529110A JP H0529110 A JPH0529110 A JP H0529110A JP 3204934 A JP3204934 A JP 3204934A JP 20493491 A JP20493491 A JP 20493491A JP H0529110 A JPH0529110 A JP H0529110A
- Authority
- JP
- Japan
- Prior art keywords
- grain boundary
- oxidation type
- boundary oxidation
- type voltage
- resistor 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.)
- Pending
Links
- 230000003647 oxidation Effects 0.000 title claims abstract description 14
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 14
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 5
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 5
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 5
- 229910052738 indium Inorganic materials 0.000 claims abstract description 4
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 4
- 229910052802 copper Inorganic materials 0.000 claims abstract description 3
- 239000003990 capacitor Substances 0.000 abstract description 4
- 229910010252 TiO3 Inorganic materials 0.000 abstract 1
- 239000002075 main ingredient Substances 0.000 abstract 1
- 229910052573 porcelain Inorganic materials 0.000 description 7
- 239000004065 semiconductor Substances 0.000 description 6
- 239000007800 oxidant agent Substances 0.000 description 5
- 229910002367 SrTiO Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 230000002159 abnormal effect Effects 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000005621 ferroelectricity Effects 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
Landscapes
- Compositions Of Oxide Ceramics (AREA)
- Thermistors And Varistors (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】この発明は粒界酸化型電圧非直線
抵抗素子に関し、特にたとえば電子機器や電気機器で発
生する異常電圧，ノイズおよび静電気などを吸収または
除去するためなどに用いられるバリスタなどのような、
粒界酸化型電圧非直線抵抗素子に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a grain boundary oxidation type voltage non-linear resistance element, and in particular, a varistor used for absorbing or removing abnormal voltage, noise and static electricity generated in electronic equipment and electric equipment. like,
The present invention relates to a grain boundary oxidation type voltage non-linear resistance element.
【０００２】[0002]
【従来の技術】従来の粒界酸化型電圧非直線抵抗素子と
しては、たとえばＳｒＴｉＯ3 系半導体磁器の結晶粒界
を空気中酸化やＮａ2 Ｏなどの酸化剤によって酸化し、
結晶粒界に絶縁層を形成したものがあった。2. Description of the Related Art As a conventional grain boundary oxidation type voltage non-linear resistance element, for example, the crystal grain boundaries of a SrTiO 3 -based semiconductor ceramic are oxidized in air or by an oxidizing agent such as Na 2 O,
In some cases, an insulating layer was formed at the grain boundaries.
【０００３】このような電圧非直線抵抗素子は、その素
体がペロブスカイト結晶構造を有し、強誘電性を示すた
め、単にバリスタとしての機能のみでなく、コンデンサ
としての機能も有する。したがって、この電圧非直線抵
抗素子を用いて、異常高電圧（サージ）の吸収や電圧の
安定化などを行うことができるという利点がある。Such a voltage non-linear resistance element has not only a function as a varistor but also a function as a capacitor because its element body has a perovskite crystal structure and exhibits ferroelectricity. Therefore, there is an advantage that the abnormal high voltage (surge) can be absorbed and the voltage can be stabilized by using the voltage nonlinear resistance element.
【０００４】[0004]
【発明が解決しようとする課題】しかしながら、従来の
ＳｒＴｉＯ3 系半導体磁器を用いたものでは、磁器を構
成する粒子間の抵抗が大きいため、その非直線係数が小
さい。また、ＳｒＴｉＯ3 系半導体磁器を用いたもので
は、パルス電圧が印加されることによって、その電気的
特性が劣化してしまう。However, in the conventional SrTiO 3 based semiconductor porcelain, the resistance between the particles forming the porcelain is large, so that the nonlinear coefficient is small. Further, in the case of using the SrTiO 3 based semiconductor porcelain, the electric characteristics thereof are deteriorated by the application of the pulse voltage.
【０００５】それゆえに、この発明の主たる目的は、バ
リスタ特性とコンデンサ特性の両方を備え、大きなバリ
スタ電圧と大きな非直線係数を有し、かつ大きなサージ
耐量を有する、粒界酸化型電圧非直線抵抗素子を提供す
ることである。Therefore, a main object of the present invention is to provide a grain boundary oxidation type voltage non-linear resistance having both varistor characteristics and capacitor characteristics, a large varistor voltage, a large non-linear coefficient, and a large surge withstand capability. It is to provide an element.
【０００６】[0006]
【課題を解決するための手段】この発明は、（Ｓｒ1-x
Ｃａx）ＴｉＯ3 （ただし、ｘ≦０．２５）を９８．０
〜９９．９モル％と、Ｎｂ，Ｗ，Ｔａ，Ｉｎおよび希土
類元素の中から選ばれる少なくとも１種類の酸化物を
０．１〜２．０モル％とからなる主成分に対して、Ｎ
ａ，ＳｉおよびＣｕ（ただし、０＜Ｎａ，０＜Ｓｉ，０
＜Ｃｕ）の酸化物が合わせて０．０１〜２．０モル％含
有されてなる、粒界酸化型電圧非直線抵抗素子である。The present invention provides (Sr 1-x
Ca x ) TiO 3 (where x ≦ 0.25) is 98.0
To 99.9 mol% and at least one oxide selected from Nb, W, Ta, In and rare earth elements in an amount of 0.1 to 2.0 mol% relative to the main component.
a, Si and Cu (where 0 <Na, 0 <Si, 0
It is a grain boundary oxidation type voltage non-linear resistance element in which an oxide of <Cu) is contained in a total amount of 0.01 to 2.0 mol%.
【０００７】[0007]
【発明の効果】この発明によれば、バリスタ特性とコン
デンサ特性の両方を備えた粒界酸化型電圧非直線抵抗素
子を得ることができる。さらに、この粒界酸化型電圧非
直線抵抗素子は、１００〜３００Ｖ程度の大きなバリス
タ電圧を得ることができ、さらに１５以上の大きな非直
線係数を得ることができる。また、この粒界酸化型電圧
非直線抵抗素子では、５０００Ａ／cm2 までのサージに
耐えることができる。According to the present invention, a grain boundary oxidation type voltage non-linear resistance element having both varistor characteristics and capacitor characteristics can be obtained. Furthermore, this grain boundary oxidation type voltage non-linear resistance element can obtain a large varistor voltage of about 100 to 300 V, and can also obtain a large non-linear coefficient of 15 or more. Further, this grain boundary oxidation type voltage non-linear resistance element can withstand a surge of up to 5000 A / cm 2 .
【０００８】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 and other objects, features and advantages of the present invention will become more apparent from the detailed description of the embodiments below.
【０００９】[0009]
【実施例】まず、ＳｒＣＯ3 ，ＴｉＯ2 ，ＣａＣＯ3お
よびＮｂ，Ｔａ，希土類元素の酸化物粉末を表１および
表２に示す組成比のものが得られるように秤量し、湿式
混合して混合物を得た。EXAMPLE First, SrCO 3 , TiO 2 , CaCO 3 and Nb, Ta, oxide powders of rare earth elements were weighed so as to obtain the composition ratios shown in Tables 1 and 2, and wet-mixed to obtain a mixture. Got
【００１０】[0010]
【表１】 [Table 1]
【表２】 [Table 2]
【００１１】この得られた混合物を乾燥後、１１５０℃
で２時間仮焼し、粉砕して粉砕物を得た。この得られた
粉砕物に酢酸ビニル系樹脂を５．０重量％添加して造粒
し、この造粒粉を１ton ／cm2 の圧力で加圧成形し、直
径１０mm，厚さ１．５mmのペレット状の成形体を得た。
この得られた成形体を空気中において１０００℃で２時
間仮焼した後、体積比でＨ2 ：Ｎ2 ＝１：１００の雰囲
気中において１４５０℃で２時間焼成し、半導体磁器を
得た。After drying the resulting mixture, it was dried at 1150 ° C.
It was calcined for 2 hours and pulverized to obtain a pulverized product. 5.0% by weight of vinyl acetate resin was added to the obtained pulverized product for granulation, and the granulated powder was pressure-molded at a pressure of 1 ton / cm 2 to give a diameter of 10 mm and a thickness of 1.5 mm. A pellet-shaped molded body was obtained.
The obtained molded body was calcined in air at 1000 ° C. for 2 hours and then calcined at 1450 ° C. for 2 hours in an atmosphere having a volume ratio of H 2 : N 2 = 1: 100 to obtain a semiconductor ceramic.
【００１２】得られた半導体磁器に、表１および表２に
示す量のＮａ2Ｏ，ＳｉＯ2 およびＣｕＯからなる酸化
剤を加え、１２００℃で２時間熱処理を行って、磁器ユ
ニットを得た。得られた磁器ユニットの対向面に銀電極
を形成し、その電気的特性を評価した。An oxidizer consisting of Na 2 O, SiO 2 and CuO in the amounts shown in Tables 1 and 2 was added to the obtained semiconductor porcelain and heat-treated at 1200 ° C. for 2 hours to obtain a porcelain unit. A silver electrode was formed on the facing surface of the obtained porcelain unit, and its electrical characteristics were evaluated.
【００１３】ここでは、磁器ユニットに１ｍＡの電流を
流した時のバリスタ電圧Ｖ1mA （Ｖ），非直線係数αお
よび５０００Ａ／cm2 のサージ電流を印加した時のバリ
スタ電圧の変化率ΔＶ1mA と非直線係数の変化率Δαと
を測定し、表３に示した。Here, the varistor voltage V 1 mA (V) when a current of 1 mA is applied to the porcelain unit and the variation rate ΔV 1 mA of the varistor voltage when a non-linear coefficient α and a surge current of 5000 A / cm 2 are applied. The non-linear coefficient change rate Δα was measured and is shown in Table 3.
【００１４】[0014]
【表３】 [Table 3]
【００１５】表１および表３の試料番号３のように、半
導体化剤としてのＮｂ，Ｗ，Ｔａ，Ｉｎおよび希土類元
素の酸化物が添加されていない場合、その電気的特性を
測定することができなかった。As shown in Sample No. 3 in Tables 1 and 3, when Nb, W, Ta, In as a semiconducting agent and an oxide of a rare earth element are not added, its electrical characteristics can be measured. could not.
【００１６】また、表１および表３の試料番号７のよう
に、半導体化剤が２．０モル％を超えた場合、サージ電
流を印加したときのバリスタ電圧変化率および非直線係
数変化率が大きくなる。Further, as in Sample No. 7 in Tables 1 and 3, when the semiconductor agent exceeds 2.0 mol%, the varistor voltage change rate and the non-linear coefficient change rate when a surge current is applied are increased. growing.
【００１７】さらに、表２および表３の試料番号１２の
ように、ｘが０．２５を超えた場合、バリスタ電圧が小
さくなるとともに、サージ電流を印加したときのバリス
タ電圧変化率および非直線係数変化率が大きくなる。Further, as in the case of sample No. 12 in Tables 2 and 3, when x exceeds 0.25, the varistor voltage decreases and the varistor voltage change rate and the nonlinear coefficient when a surge current is applied. The rate of change increases.
【００１８】また、表２および表３の試料番号１３のよ
うに、酸化剤の添加量が０．０１モル％より少ない場
合、バリスタ電圧および非直線係数が小さくなる。When the amount of the oxidizing agent added is less than 0.01 mol%, as in sample No. 13 in Tables 2 and 3, the varistor voltage and the nonlinear coefficient are small.
【００１９】さらに、表２および表３の試料番号１４〜
１６のように、Ｎａ2 Ｏ，ＳｉＯ2 ，ＣｕＯをそれぞれ
単独で添加した場合、バリスタ電圧および非直線係数が
小さくなる。Further, sample numbers 14 to 14 in Tables 2 and 3
When Na 2 O, SiO 2 and CuO are individually added as in No. 16, the varistor voltage and the non-linear coefficient become small.
【００２０】また、表２および表３の試料番号１９のよ
うに、酸化剤の添加量が２．０モル％を超えた場合、サ
ージ電流を印加したときのバリスタ電圧変化率および非
直線係数変化率が大きくなる。Further, as in the case of sample No. 19 in Tables 2 and 3, when the amount of oxidant added exceeds 2.0 mol%, the varistor voltage change rate and the nonlinear coefficient change when a surge current is applied. The rate increases.
【００２１】それに対して、この発明の粒界酸化型電圧
非直線抵抗素子では、５０００Ａ／cm2 までのサージ電
流に耐えることができ、かつ非直線係数αが１５以上と
大きい。On the other hand, the grain boundary oxidation type voltage non-linear resistance element of the present invention can withstand a surge current up to 5000 A / cm 2 and has a large non-linear coefficient α of 15 or more.
【００２２】また、酸化剤としてＮａおよびＳｉの酸化
物を用いた場合、非直線係数が従来のものの１．５倍程
度になり、安定性にも優れたものとなる。さらに、Ｃｕ
Ｏを加えた場合、サージ耐量や非直線係数をさらに大き
くすることができる。When Na and Si oxides are used as the oxidizing agent, the non-linear coefficient is about 1.5 times that of the conventional one, and the stability is excellent. In addition, Cu
When O is added, the surge resistance and the nonlinear coefficient can be further increased.
【００２３】また、静電容量は、ＣｕＯの添加量によっ
てコントロールすることができ、粒界酸化型電圧非直線
抵抗素子の生産に好適である。The capacitance can be controlled by the amount of CuO added, which is suitable for the production of grain boundary oxidation type voltage non-linear resistance elements.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 坂 部 行 雄 京都府長岡京市天神二丁目26番10号 株式 会社村田製作所内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yukio Sakabe 2-10-10 Tenjin 2-10, Tenjin, Nagaokakyo, Kyoto Prefecture Murata Manufacturing Co., Ltd.
Claims (1)
ｘ≦０．２５）を９８．０〜９９．９モル％と、Ｎｂ，
Ｗ，Ｔａ，Ｉｎおよび希土類元素の中から選ばれる少な
くとも１種類の酸化物を０．１〜２．０モル％とからな
る主成分に対して、Ｎａ，ＳｉおよびＣｕ（ただし、０
＜Ｎａ，０＜Ｓｉ，０＜Ｃｕ）の酸化物が合わせて０．
０１〜２．０モル％含有されてなる、粒界酸化型電圧非
直線抵抗素子。Claims: (Sr 1-x Ca x ) TiO 3 (however,
x ≦ 0.25) of 98.0 to 99.9 mol% and Nb,
W, Ta, In and at least one oxide selected from rare earth elements are contained in an amount of 0.1 to 2.0 mol%, and Na, Si and Cu (however, 0
<Na, 0 <Si, 0 <Cu) oxides are 0.
A grain boundary oxidation type voltage non-linear resistance element containing 0.1 to 2.0 mol%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3204934A JPH0529110A (en) | 1991-07-19 | 1991-07-19 | Grain boundary oxidation type voltage nonlinear resistor element |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3204934A JPH0529110A (en) | 1991-07-19 | 1991-07-19 | Grain boundary oxidation type voltage nonlinear resistor element |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0529110A true JPH0529110A (en) | 1993-02-05 |
Family
ID=16498778
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3204934A Pending JPH0529110A (en) | 1991-07-19 | 1991-07-19 | Grain boundary oxidation type voltage nonlinear resistor element |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0529110A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016108231A (en) * | 2014-12-08 | 2016-06-20 | 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 |
-
1991
- 1991-07-19 JP JP3204934A patent/JPH0529110A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016108231A (en) * | 2014-12-08 | 2016-06-20 | 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 |
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