JPH03138905A - Voltage dependent non-linear ceramic resistor and its manufacture - Google Patents
Voltage dependent non-linear ceramic resistor and its manufactureInfo
- Publication number
- JPH03138905A JPH03138905A JP1277424A JP27742489A JPH03138905A JP H03138905 A JPH03138905 A JP H03138905A JP 1277424 A JP1277424 A JP 1277424A JP 27742489 A JP27742489 A JP 27742489A JP H03138905 A JPH03138905 A JP H03138905A
- Authority
- JP
- Japan
- Prior art keywords
- voltage
- mol
- mgo
- varistor
- temperature
- 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
- 239000000919 ceramic Substances 0.000 title claims abstract description 8
- 230000001419 dependent effect Effects 0.000 title claims description 9
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 150000003839 salts Chemical class 0.000 claims description 14
- 239000012298 atmosphere Substances 0.000 claims description 9
- 229910052573 porcelain Inorganic materials 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000003973 paint Substances 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 229910002370 SrTiO3 Inorganic materials 0.000 abstract description 15
- 239000011656 manganese carbonate Substances 0.000 abstract description 7
- 235000006748 manganese carbonate Nutrition 0.000 abstract description 7
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 abstract description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 6
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 abstract description 6
- 230000005611 electricity Effects 0.000 abstract description 6
- 239000000203 mixture Substances 0.000 abstract description 6
- 230000003068 static effect Effects 0.000 abstract description 6
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 abstract description 5
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052681 coesite Inorganic materials 0.000 abstract description 4
- 229910052906 cristobalite Inorganic materials 0.000 abstract description 4
- 229910052682 stishovite Inorganic materials 0.000 abstract description 4
- 229910052905 tridymite Inorganic materials 0.000 abstract description 4
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 abstract description 3
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 abstract description 3
- 230000007547 defect Effects 0.000 abstract description 2
- -1 CO2O3 Substances 0.000 abstract 2
- 239000000377 silicon dioxide Substances 0.000 abstract 2
- 235000012239 silicon dioxide Nutrition 0.000 abstract 2
- 229910006710 Li—P Inorganic materials 0.000 abstract 1
- 229910008332 Si-Ti Inorganic materials 0.000 abstract 1
- 229910006749 Si—Ti Inorganic materials 0.000 abstract 1
- 230000008030 elimination Effects 0.000 abstract 1
- 238000003379 elimination reaction Methods 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 15
- 239000004065 semiconductor Substances 0.000 description 15
- 238000005245 sintering Methods 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 9
- UPWOEMHINGJHOB-UHFFFAOYSA-N oxo(oxocobaltiooxy)cobalt Chemical compound O=[Co]O[Co]=O UPWOEMHINGJHOB-UHFFFAOYSA-N 0.000 description 8
- 238000010304 firing Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 230000007423 decrease Effects 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 239000003990 capacitor Substances 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000005469 granulation Methods 0.000 description 3
- 230000003179 granulation Effects 0.000 description 3
- 238000010405 reoxidation reaction Methods 0.000 description 3
- 230000002159 abnormal effect Effects 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000000889 atomisation Methods 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000009766 low-temperature sintering Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229910000018 strontium carbonate Inorganic materials 0.000 description 2
- LEDMRZGFZIAGGB-UHFFFAOYSA-L strontium carbonate Chemical compound [Sr+2].[O-]C([O-])=O LEDMRZGFZIAGGB-UHFFFAOYSA-L 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910017583 La2O Inorganic materials 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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、電子機器、電子機器で発生する異常高電圧、
ノイズ、パルス、静電気から半導体装置回路を保護する
ところのＳｒＴｉＯ３を主成分とする電圧依存性非直線
抵抗体磁器及びその製造方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to electronic equipment, abnormal high voltage generated in electronic equipment,
The present invention relates to a voltage-dependent nonlinear resistor ceramic whose main component is SrTiO3, which protects semiconductor device circuits from noise, pulses, and static electricity, and a method for manufacturing the same.
従来の技術
従来、各種電子機器、電子機器で発生する異常高電圧、
ノイズ、パルス、静電気除去のためにバリスタ特性を有
するＳｉＣバリスタやＺｎＯ系バリスタが使用されてき
た。このようなバリスタの電圧−電流特性は近似的に次
式のように表すことができる。Conventional technology Conventionally, various electronic devices, abnormal high voltages generated in electronic devices,
SiC varistors and ZnO-based varistors having varistor characteristics have been used to remove noise, pulses, and static electricity. The voltage-current characteristics of such a varistor can be approximately expressed as in the following equation.
１＝（Ｖ／Ｃ）α
ここで、■は電流、■は電圧、Ｃはバリスタ固有の定数
であり、αは電圧非直線指数である。1=(V/C) α Here, ■ is a current, ■ is a voltage, C is a constant specific to the varistor, and α is a voltage nonlinear index.
ＳｉＣバリスタの電圧非直線指数αは２〜７程度、Ｚｎ
Ｏ系バリスタではαが５０にも及ぶものがある。このよ
うなバリスタは、比較的高い電圧の吸収には優れた性能
を有しているが、誘電率が低く、固有の静電容量が小さ
いためバリスタ電圧以下の低い電圧や周波数の高いもの
の吸収に対してはほとんど効果を示さない。また、誘電
損失ｔａｎδが５〜１０％と大きい。The voltage non-linearity index α of SiC varistor is about 2 to 7, Zn
Some O-type varistors have α as high as 50. Although such varistors have excellent performance in absorbing relatively high voltages, their low dielectric constant and small inherent capacitance make them difficult to absorb low voltages below the varistor voltage or high frequencies. It has almost no effect on Further, the dielectric loss tan δ is as large as 5 to 10%.
一方、低電圧のノイズなどの除去には、見掛は誘電率ε
が５Ｘ１０４程度で、誘電損失ｔａｎδが１％前後の半
導体コンデンサが利用されている。しかし、このような
半導体コンデンサは、サージなどによりある限度以上の
電圧、電流が印加されると破壊したり、コンデンサとし
ての機能を果たさなくなる。そこで、近年５ｒＴｉ（ｈ
を主成分とし、バリスタ特性と、コンデンサ特性の両方
の機能を有するものが開発されている。On the other hand, to remove low-voltage noise, etc., the apparent dielectric constant ε
A semiconductor capacitor with a dielectric loss tan δ of about 1% is used. However, such semiconductor capacitors break down or cease to function as a capacitor when a voltage or current exceeding a certain limit is applied due to a surge or the like. Therefore, in recent years, 5rTi (h
A device has been developed that has both varistor characteristics and capacitor characteristics.
発明が解決しようとする課題
ＳｒＴｉＯ３を主成分とする容量性バリスタは、バリス
タ電圧が高い、電圧非直線指数αが小さい、見掛は誘電
率εが小さい、容量温度特性が良くないと言う問題を有
しており、全ての特性を同時に満足するものは未だに得
られていない。さらに、焼結温度、再酸化温度が高いこ
とからエネルギー量の消費が多いと言う問題を有してい
る。Problems to be Solved by the Invention Capacitive varistors whose main component is SrTiO3 have the following problems: high varistor voltage, small voltage nonlinearity index α, apparently small dielectric constant ε, and poor capacitance-temperature characteristics. However, a product that satisfies all of the characteristics simultaneously has not yet been obtained. Furthermore, since the sintering temperature and reoxidation temperature are high, there is a problem in that a large amount of energy is consumed.
従って、ＳｒＴｉＯ３を主成分とする容量性バリスタに
おいて、バリスタ電圧が低い、電圧非直線指数αが大き
い、見掛は誘電率εが大きい、容量温度特性が良いと言
う条件を同時に満たし、さらに、焼成時や再酸化温度が
低温で行える必要がある。本発明は、このような点に鑑
みてなされたもので、低電圧のノイズなどの除去が可能
なＳｒＴｉＯ３を主成分とする電圧依存性非直線抵抗体
磁器及びその製造方法を提供することを目的とするもの
である。Therefore, in a capacitive varistor whose main component is SrTiO3, the conditions of low varistor voltage, large voltage non-linearity index α, large apparent dielectric constant ε, and good capacitance temperature characteristics are simultaneously satisfied, and furthermore, the varistor It is necessary to perform the reoxidation at a low time and reoxidation temperature. The present invention has been made in view of these points, and an object of the present invention is to provide a voltage-dependent nonlinear resistor ceramic whose main component is SrTiO3, which can eliminate low-voltage noise, and a method for manufacturing the same. That is.
課題を解決するための手段
上記のような課題を解決するために本発明は、ＳｒとＴ
ｉの比が１．００１≦Ｓｒ／Ｔｉ≦１．０５となるよう
に過剰のＳｒを含有し、さらにＬｉとＦを合計で０．０
０７〜０．５００ｗｔ％含有したＳｒＴｉＯ３に、Ｃｅ
Ｏ２，Ｙ２Ｏ３Ｔ Ｌａｚｏｓのうち少なくとも一種類
以上を０．１〜２．０ｍｏ １％とＳ ｉ０２．Ｃｕｂ
、Ｃｏ２０ｓ、ＭｎＣＯ３のうち少なくとも一種類以上
を０．１〜２．０ｍｏ １％とＢａＯ，Ｃａｂ、ＭｇＯ
のうち少なくとも一種類以上を０．１〜１．０ｍｏｌ％
含ませてなる磁器であり、その磁器に含まれる水溶性塩
が０．０５０ｗｔ％以下とした電圧依存性非直線抵抗体
磁器を提供するものである。また、本発明は、平均粒径
が０．５μｍ以下の５ｒＴｉ（ｈ粉末を原料として１．
００１≦Ｓｒ／Ｔｉ≦１．０５となるようにＳｒ化合物
を添加し、さらに、ＬｉＦ０．７〜７．０ｍｏｌ％とＣ
ｅＯ２，Ｙ２Ｏ３，Ｌａｚｏｓのうち少なくとも一種類
以上を０．１〜２．０ｍｏ １％とＳ ｉ０２．Ｃｕｂ
、Ｃｏ２Ｏ３，ＭｎＣ０ａのうち少なくとも一種類以上
を０．１〜２．０ｍｏ １％とＢａＯ，Ｃａｂ、ＭｇＯ
のうち少なくとも一種類以上を０．１〜１．０ｍｏ １
％添加した混合粉末を成形し、還元雰囲気中で１０００
℃〜１４００℃の温度で焼成し、その後、空気中で５０
０〜１０００℃の熱処理または後電極を設けるか、また
は、５００〜９００℃で焼き付け可能な銀ペイントを焼
き付けた磁器に含まれる水溶性塩が０．０５０ｗｔ％以
下とした電圧依存性非直線抵抗体磁器の製造方法を提供
するものである。Means for Solving the Problems In order to solve the above problems, the present invention provides Sr and T.
Contains excess Sr such that the ratio of i is 1.001≦Sr/Ti≦1.05, and further contains Li and F in a total of 0.0
Ce
At least one type of O2, Y2O3T Lazos with 0.1 to 2.0mo 1% and Si02. Cub
, Co20s, MnCO3 with 0.1-2.0mo 1% and BaO, Cab, MgO
0.1 to 1.0 mol% of at least one type of
The object of the present invention is to provide a voltage-dependent nonlinear resistor porcelain in which the water-soluble salt contained in the porcelain is 0.050 wt% or less. Further, the present invention uses 5rTi (h powder) having an average particle size of 0.5 μm or less as a raw material and 1.
Sr compound is added so that 001≦Sr/Ti≦1.05, and LiF0.7 to 7.0 mol% and C
At least one of eO2, Y2O3, and Lazos at 0.1 to 2.0mo 1% and Si02. Cub
, Co2O3, MnC0a at 0.1-2.0mo 1% and BaO, Cab, MgO
0.1 to 1.0 mo 1 of at least one type of
% added mixed powder was molded and 1000% added in a reducing atmosphere.
Calcinate at a temperature of ℃~1400℃, then 50℃ in air.
A voltage-dependent nonlinear resistor in which the water-soluble salt contained in the porcelain is heat-treated at 0 to 1000°C or provided with a post-electrode, or baked with silver paint that can be baked at 500 to 900°C, and the water-soluble salt is 0.050 wt% or less. A method for manufacturing porcelain is provided.
作用
一般にＳｒＴｉＯ３を半導体化させるには、強制還元す
るか、もしくか半導体化促進剤を添加し還元雰囲気焼成
するかである。しかし、これだけでは半導体化促進剤の
種類によって半導体化が進まない場合がある。そこで、
ＳｒＴｉＯ３を化学量論よりＳｒ過剰、または、Ｔｉ過
剰にすると格子欠陥が増加し半導体化が促進される。さ
らに、Ｓｒを他の元素、Ｃｅ、Ｙ、Ｌａで置換すると原
子化制御により半導体化が促進される。また、Ｓｒを他
の元素、Ｂ ａ Ｔ ｅ ａ ２Ｍ ｇで置換すると結
晶構造に歪みを生じ半導体化が促進される。Function Generally, in order to convert SrTiO3 into a semiconductor, it is either forcedly reduced, or a semiconductor conversion accelerator is added and fired in a reducing atmosphere. However, with this alone, semiconductor formation may not proceed depending on the type of semiconductor formation accelerator. Therefore,
When SrTiO3 is made to have an excess of Sr or an excess of Ti compared to the stoichiometry, lattice defects increase and semiconductor formation is promoted. Furthermore, when Sr is replaced with other elements such as Ce, Y, and La, semiconductor formation is promoted through atomization control. Furthermore, when Sr is replaced with another element, B a T e a 2 M g, the crystal structure is distorted and semiconductor formation is promoted.
次に、Ｓ ｉ ０２．Ｃｕｂ、Ｃｏ２Ｏ３，ＭｎＣＯ３
を添加すると、これらが粒界に偏析し、粒界を高抵抗化
させ、バリスタ特性を発現させる。Next, S i 02. Cub, Co2O3, MnCO3
When added, these segregate at the grain boundaries, making the grain boundaries high in resistance and exhibiting varistor properties.
またさらに、この時、本発明のようにＬｉＦを添加し、
窒素雰囲気や還元雰囲気中で焼成すると、５８０℃付近
でＳ ｒｏ−Ｔ ｉ０２− Ｌ ｉ Ｆ系の液相を形成
し、液相焼結により焼結が促進される。また、この液相
を介して５ｒＴｉ○３が溶解析出し粒成長が起こる。こ
れにより低温焼結が可能な焼結体素子を得ることができ
、焼結のためのエネルギー量を削減することができるこ
ととなる。Furthermore, at this time, LiF is added as in the present invention,
When fired in a nitrogen atmosphere or a reducing atmosphere, a S ro-T i02- Li F-based liquid phase is formed at around 580° C., and sintering is promoted by liquid phase sintering. In addition, 5rTi○3 is dissolved and separated and grains grow through this liquid phase. As a result, it is possible to obtain a sintered body element that can be sintered at a low temperature, and the amount of energy for sintering can be reduced.
しかし、ここでＴｉ過剰であるとＬｉ２Ｔｉ（ｈを形成
するため５ｒＴｉ（ｈの焼結性が抑制される。However, if Ti is excessive here, the sinterability of 5rTi(h) is suppressed because Li2Ti(h) is formed.
従って、Ｓｒ過剰が望まれる。しかし、Ｓｒ過剰もある
限度を越すと粒成長が抑制され焼結性が低下することや
、焼結体素子に水溶性塩を過剰に含むため信頼性や寿命
特性に影響を与える。Therefore, excess Sr is desired. However, if excess Sr exceeds a certain limit, grain growth will be suppressed and sinterability will deteriorate, and the sintered element will contain an excessive amount of water-soluble salt, which will affect reliability and life characteristics.
また、ＳｒＴｉＯ３に対するＬｉＦの添加量は焼成温度
と密接に関係しており、低温焼結のためには、ある程度
以上のＬｉＦを添加しなければならない、そして、この
場合、添加したＬｉＦが焼成中に飛散し、これによって
焼成用のサヤ、炉壁２発熱体などが侵されたり、信頼性
や寿命特性を著しく低下させるという実用上の開題点を
有している。しかし、本発明者らは研究の結果、第１図
に示すように５ｒＴｉ（ｈの原料粒径を微細化して０．
５μｍ以下の原料を用いることにより、ＬｉＦの添加量
を低減しても低温焼結が可能であることを見出した。従
って、このことから焼成時のＬｉＦの飛散、残存量の抑
制、および焼結体素子の信頼性や寿命特性を向上させる
ことが可能である。In addition, the amount of LiF added to SrTiO3 is closely related to the firing temperature, and for low-temperature sintering, a certain amount of LiF must be added. This poses a practical problem in that it scatters and damages the firing sheath, the heating element of the furnace wall 2, etc., and significantly reduces reliability and life characteristics. However, as a result of our research, the inventors of the present invention found that by refining the raw material particle size of 5rTi (h), as shown in FIG.
It has been found that by using raw materials with a diameter of 5 μm or less, low-temperature sintering is possible even when the amount of LiF added is reduced. Therefore, from this, it is possible to suppress the scattering and residual amount of LiF during firing and to improve the reliability and life characteristics of the sintered element.
次に、還元雰囲気焼成の温度を１０００〜１４００℃に
規定したのは、第２図に示すように１０００℃未満では
焼結体素子に含まれるＬｉとＦの残存量が０．５００ｗ
ｔ％よりも多いため信頼性や電気特性に影響を与えるこ
とと、焼結密度が低いためである。また、１４００℃を
超えると多孔質となり焼成密度が低下するためである。Next, the temperature for firing in a reducing atmosphere was set at 1000 to 1400°C because, as shown in Figure 2, below 1000°C, the residual amount of Li and F contained in the sintered element is 0.500w.
This is because the amount is higher than t%, which affects reliability and electrical characteristics, and because the sintered density is low. In addition, if the temperature exceeds 1400°C, it becomes porous and the firing density decreases.
従って、Ｓｒ過剰の５ｒＴｉＯｓにＣｅＯ２゜Ｙ ２０
３１ Ｌ ａ ２０３のうち少なくとも一種類以上とＳ
ｉ０２．Ｃｕｂ、Ｃｏ２Ｏ３，ＭｎＣＯ３のうち少な
くとも一種類以上と、ＢａＯ，Ｃａｂ、ＭｇＯのうち少
なくとも一種類以上を添加して得られた焼結体とＳｒ過
剰の５ｒＴｉＯｓにＣｅＯ２゜Ｙ２Ｏ５，Ｌａ２Ｏ３の
うち少なくとも一種類以上とＳ ｉｏｚ、Ｃｕｂ、Ｃｏ
２Ｏ３，ＭｎＣＯ３のうち少なくとも一種類以上とＢ
ａ Ｏ、Ｃａ Ｏ、Ｍ ｇ Ｏのうち少なくとも一種類
以上及びＬｉＦを添加し最終的に得られる焼結体とでは
、微細構造、電気特性が著しく異なり、互いにして全く
別の組成物であると考えられる。Therefore, in 5rTiOs with excess Sr, CeO2゜Y20
31 At least one type of L a 203 and S
i02. A sintered body obtained by adding at least one type of Cub, Co2O3, MnCO3 and at least one type of BaO, Cab, MgO, and at least one type of CeO2゜Y2O5, La2O3 to 5rTiOs with excess Sr. Above and S ioz, Cub, Co
At least one or more of 2O3, MnCO3 and B
The microstructure and electrical properties of the sintered body finally obtained by adding at least one of aO, CaO, MgO and LiF are completely different compositions. it is conceivable that.
実施例 以下に本発明の実施例を上げて具体的に説明する。Example EXAMPLES The present invention will be described in detail below using examples.
（実施例１）
まず、ＳｒＴｉＯ３とＳｒＣＯ３と第１成分のＣｅ０２
１ Ｙ２Ｏ３１Ｌａ２Ｏ３と第２成分の５ｉ０２と第３
成分のＣａＯ及びＬｉＦを第１表に示す組成比になるよ
うに秤量し、混合する。乾燥後、０．５ｗｔ％ポリビニ
ールアルコール溶液のバインダーを添加し、１時間混合
し造粒する。造粒後、１ｔｏｎ／ｃｊの圧力で１２φＸ
１．Ｏ（＋ｎｍ）の円板状に成形し、次に、空気中で４
００℃、１時間脱バインダーを行う。その後、Ｎ２：
Ｈ２＝ｌＯ： １の還元雰囲気中で１０００〜１４００
℃、２時間焼成する。このようにして得られた第３図、
第４図に示す焼結体１の両面に、外周を残すようにして
Ａｇなどの導電性ペーストをスクリーン印刷し５００〜
９００℃、１０〜６０分の条件で焼き付け電極２，３を
形成する。このようにして得られた、還元雰囲気中で１
３００℃、２時間焼成した素子の電気特性、さらに、素
子内部に含まれるＬｉ。(Example 1) First, SrTiO3, SrCO3 and the first component Ce02
1 Y2O31La2O3 and the second component 5i02 and the third
The components CaO and LiF are weighed and mixed so as to have the composition ratio shown in Table 1. After drying, a binder of 0.5 wt% polyvinyl alcohol solution is added, mixed for 1 hour, and granulated. After granulation, 12φX at a pressure of 1 ton/cj
1. Formed into a disc of O (+nm), then heated in air for 4 hours.
Binder removal is performed at 00°C for 1 hour. Then N2:
H2=lO: 1000-1400 in a reducing atmosphere of 1
Bake at ℃ for 2 hours. Figure 3 obtained in this way,
A conductive paste such as Ag is screen printed on both sides of the sintered body 1 shown in Fig. 4, leaving the outer periphery.
Baked electrodes 2 and 3 are formed at 900° C. for 10 to 60 minutes. 1 in a reducing atmosphere obtained in this way.
Electrical properties of the device fired at 300°C for 2 hours, and Li contained inside the device.
Ｆ、Ｓｒ＋ Ｂａ、Ｃａ、Ｍｇ原子を含む水溶性塩の含
量及び信頼性試験の結果を第２表に示す。ここで、素子
内部に含まれる水溶性塩の含量は、次の方法により解析
した。まず焼結した素子を粉砕し、それに水を加え１０
分間煮沸する。ろ過後、Ｌｉ、Ｓｒ、Ｂａ、Ｃａ、Ｍｇ
はフレーム原子吸光、Ｆはイオン電極法により調べた。The content of water-soluble salts containing F, Sr+ Ba, Ca, Mg atoms and the results of reliability tests are shown in Table 2. Here, the content of water-soluble salt contained inside the element was analyzed by the following method. First, crush the sintered element and add water to it for 10 minutes.
Boil for minutes. After filtration, Li, Sr, Ba, Ca, Mg
was investigated by flame atomic absorption, and F was investigated by ion electrode method.
さらに信頼性試験の評価法として、焼結した素子を温度
９０℃、湿度９０〜９５％の耐湿雰囲気中に５００時間
放置した後、素子を取り出し室温中に４８時間放置した
後、容量変化率を求めた。Furthermore, as an evaluation method for reliability testing, the sintered element was left in a humidity-resistant atmosphere with a temperature of 90°C and a humidity of 90 to 95% for 500 hours, and then the element was taken out and left at room temperature for 48 hours, and the rate of change in capacity was measured. I asked for it.
（以 下 余 白 ）
まず、第１．第２表について解説すると、試料ＮＱＩ〜
９．１６，１７．２２〜２４．３１〜３３゜３６．３７
．４４〜５２は比較例である。これらの焼結体素子では
密度が、３．５〜４゜９ ｇ ／ ｃ＋ｊ（理論密度の
６７〜９４％）と低いためバリスタとしての特性に適し
ていないもの、または、容量変化率が大きく信頼性や電
気特性が低下しバリスタとしての適していないものであ
る。これに対し、その他の本発明にかかる試料ｆｆ１ｌ
ｏ〜１５゜１８〜２１．２５〜３０．３４．３５．３８
〜４３では、焼結密度が５．０ｇ／−以上（理論密度の
９６％以上）と高くバリスタとしての特性に適している
ものである。さらに、容量変化率が小さく信頼性や電気
特性が低下せずバリスタとしての特性に適しているもの
である。(Left below) First, 1st. To explain Table 2, sample NQI~
9.16, 17.22~24.31~33°36.37
．． 44 to 52 are comparative examples. These sintered elements have low densities of 3.5 to 4°9 g/c+j (67 to 94% of the theoretical density), making them unsuitable for characteristics as varistors, or their capacitance change rates are too large to be reliable. Its properties and electrical properties deteriorate, making it unsuitable for use as a varistor. In contrast, other samples ff1l according to the present invention
o~15°18~21.25~30.34.35.38
-43 has a high sintered density of 5.0 g/- or more (96% or more of the theoretical density) and is suitable for characteristics as a varistor. Furthermore, the capacitance change rate is small and the reliability and electrical characteristics do not deteriorate, making it suitable for characteristics as a varistor.
ここでＬｉとＦの残存量を規定したのは、ＬｉとＦはＳ
ｒＴｉＯ３と反応し５ｒＯ−Ｔｔ０２−ＬｉＦ系の液相
を形成する。モして液相焼結により焼結性を促進させる
効果を示すが、残存量が、０．００７ｗｔ％未満である
Ｓｒ／Ｔｉ比１．０２゜ＣｅＯ２，Ｙ２Ｏ３，Ｌａｇ０
３．Ｓ ｉ０２．ＣａＯ各０．２ｍｏ１％、Ｌ ｉ Ｆ
０．１ｍｏ １％を添加し、焼成温度１４００℃、２時
間で焼成した素子焼結密度が向上せずＬｉＦの添加効果
が得られないためである。一方、残存量が０．５００ｗ
ｔ％を超えるＳｒ／Ｔｉ比１．０２．ＣｅＯ２，Ｙ２Ｏ
３゜Ｌａ２Ｏ５，Ｓ ｉ０２．ＣａＯ各０．２ｍｏ １
％。Here, the residual amounts of Li and F were specified because Li and F are S
It reacts with rTiO3 to form a 5rO-Tt02-LiF system liquid phase. However, the residual amount is less than 0.007wt% Sr/Ti ratio 1.02゜CeO2, Y2O3, Lag0
3. S i02. CaO each 0.2mol1%, LiF
This is because the sintered density of the element which was added with 1% of LiF and fired at a firing temperature of 1400° C. for 2 hours was not improved and the effect of adding LiF could not be obtained. On the other hand, the remaining amount is 0.500w
Sr/Ti ratio exceeding t% 1.02. CeO2, Y2O
3゜La2O5,S i02. CaO each 0.2mo 1
%.
ＬｉＦｌ０．０ｍｏｌ％を添加し、焼成温度１０００℃
、２時間で焼成した素子では素子が多孔質となり焼結密
度が低下することと、素子内部にＬｉ２Ｆ原子を含む水
溶性塩の含量が増加し、信頼性や電気特性が低下するた
めである。Added 0.0 mol% of LiFl and fired at a temperature of 1000°C.
This is because an element fired for 2 hours becomes porous and the sintered density decreases, and the content of water-soluble salts containing Li2F atoms increases inside the element, resulting in a decrease in reliability and electrical properties.
次にＳｒＴｉＯ３のＳ ｒ ／ Ｔ ｉ比を１．００１
〜１．０５に規定したのは、Ｓｒ／Ｔｉ比が１．００１
未満では試料隘１〜８に示すように焼結密度が向上しな
いためである。これは焼結過程でＬ ｉ ２Ｔ ｉ ０
３を形成するためにＳｒＴｉＯ３の焼結性を抑制するた
めと考えられる。一方、Ｓ ｒ ／ Ｔ ｉ比が１．０
５を超えると試料歯４４〜５２に示すように焼結密度が
向上しない。これは、Ｓｒの含量が増え過ぎたため粒成
長が抑制され焼結性が低下するためである。またこの場
合、素子内部にＳｒ原子を含む水溶性塩の含量が増加し
、信頼性や電気特性が低下するためである。Next, the Sr/Ti ratio of SrTiO3 was set to 1.001.
~1.05 is specified when the Sr/Ti ratio is 1.001.
This is because the sintered density does not improve as shown in samples Nos. 1 to 8 below. This is during the sintering process L i 2T i 0
This is considered to be because the sinterability of SrTiO3 is suppressed to form SrTiO3. On the other hand, when the S r / T i ratio is 1.0
If it exceeds 5, the sintered density will not improve as shown in sample teeth 44-52. This is because the Sr content increases too much, which suppresses grain growth and reduces sinterability. Further, in this case, the content of water-soluble salts containing Sr atoms inside the element increases, resulting in a decrease in reliability and electrical characteristics.
また、第１成分のＣｅＯ２，Ｙ２Ｏ３，Ｌａ２Ｏ３の添
加量を規定したのは、Ｃｅ２０ｓ、Ｙ２Ｏ３゜Ｌａ２Ｏ
３は、ＳｒＴｉＯ３中のＳｒと置換し原子化制御により
半導体化を促進させる効果を示すが、少なくとも一種類
以上がＯ，１ｍｏ １％未満では、試料歯２２，２３．
２４に示すように添加効果が得られず。半導体化が抑制
され誘電率が劣化し、またバリスタ電圧が大きいため、
高容量。In addition, the addition amounts of the first components CeO2, Y2O3, and La2O3 were determined by Ce20s, Y2O3°La2O
3 shows the effect of replacing Sr in SrTiO3 and promoting semiconductor formation by controlling atomization, but if at least one type is O, 1mo less than 1%, sample teeth 22, 23.
As shown in No. 24, the addition effect was not obtained. Semiconducting is suppressed, the dielectric constant deteriorates, and the varistor voltage is large, so
High capacity.
低バリスタ電圧の特徴を示さないためである。−方、２
．０ｍｏｌ％を超えると、試料ＮＱ３１．３２゜３３に
示すように半導体化が抑制されることと、焼結性が低下
するためである。This is because it does not exhibit the characteristics of low varistor voltage. - direction, 2
．． This is because if it exceeds 0 mol %, semiconductor formation is suppressed and sinterability is reduced as shown in sample NQ31.32°33.
さらに、素子内部に含まれる水溶性塩の含量を０．０５
０ｗｔ％以下と規定したのは、０．０５０ｗ ｔ ９６
を超えると下記第５図に示すように耐湿雰囲気中での容
量変化率が上昇し信頼性や電気特性が低下するためであ
る。Furthermore, the content of water-soluble salt contained inside the element was reduced to 0.05.
0.050wt96 is defined as 0wt% or less.
This is because, if it exceeds this value, as shown in FIG. 5 below, the rate of change in capacity in a humidity-resistant atmosphere increases and reliability and electrical characteristics deteriorate.
次に、焼成温度を１０００〜１４００℃に規定したのは
第２図に示すように１０００℃未満では焼結体素子に含
まれるＬｉとＦの残存量が０．５００ｗｔ％よりも多い
ため信頼性や電気特性に影響を与えることと、焼結密度
が低いためである。また１４００℃を超えると多孔質と
なり焼結密度が低下するためである。Next, the firing temperature was set at 1000 to 1400°C because, as shown in Figure 2, if the temperature is lower than 1000°C, the residual amount of Li and F contained in the sintered element is more than 0.500 wt%, so reliability is low. This is because the sintering density is low, and the sintering density is low. Moreover, if the temperature exceeds 1400°C, the sintered density becomes porous and the sintered density decreases.
（実施例２）
次に、第３表に示すように第２成分の
Ｓ ｉ ０２． Ｃｕ Ｏｒ Ｃ０２０３，Ｍｎ ＣＯ
３の組成をかえて、実施例１と同様の方法で混合、造粒
、成形、電極焼き付けを行い、第４表に示すように各種
特性を測定した。(Example 2) Next, as shown in Table 3, the second component S i 02. Cu Or C0203, Mn CO
Mixing, granulation, molding, and electrode baking were performed in the same manner as in Example 1, except that the composition of Example 3 was changed, and various properties were measured as shown in Table 4.
（以 下 余 白 ）
まず、第３．第４表について解説すると、試料ＮＱ１〜
４，１５〜１８は比較例である。これに対し、その他の
本発明にかかる試料１５〜１４はＳ １０２１ Ｃｕ
Ｏｒ ＣＯ２０３１Ｍ ｎ ＣＯ３の添加効果が得られ
るものである。ここで、第２成分のＳ ｉｏｚ、Ｃｕｂ
、ＣＯ２Ｏ３，ＭｎＣＯ３の添加量を規定したのは、こ
れらの添加剤を添加すると、これらが粒界に偏析し、粒
界を高抵抗化させ、バリスタ特性を発現させる効果を示
すが、０．１ｍｏ１％未満では、試料歯１〜４に示すよ
うにバリスタ特性を改善する効果がないためである。(Margin below) First, 3rd. To explain Table 4, samples NQ1~
4, 15 to 18 are comparative examples. On the other hand, other samples 15 to 14 according to the present invention are S 1021 Cu
The effect of adding Or CO2031M n CO3 can be obtained. Here, the second component S ioz, Cub
, CO2O3, and MnCO3 were specified because when these additives are added, they segregate at the grain boundaries, increase the resistance of the grain boundaries, and exhibit the effect of developing varistor characteristics. This is because if it is less than %, there is no effect of improving the varistor characteristics as shown in sample teeth 1 to 4.
方２．０ｍｏｌ％を超えると試料嵐１５〜１８に示すよ
うに粒界にこの添加剤が極端に偏析し、バリスタ電圧が
上昇すると共に誘電率や焼結密度が低下するためである
。This is because if the content exceeds 2.0 mol %, this additive will segregate to the grain boundary extremely as shown in Sample Arashi 15 to 18, and the varistor voltage will increase and the dielectric constant and sintered density will decrease.
（実施例３） 次に、第５表に示すように、第３成分のＢａＯ。(Example 3) Next, as shown in Table 5, the third component BaO.
Ｃａｂ、ＭｇＯの組成をかえて、実施例１，２と同様の
方法で混合、造粒、成形、電極焼き付けを行い、第６表
に示すように各種特性を測定した。Mixing, granulation, molding, and electrode baking were performed in the same manner as in Examples 1 and 2, with different compositions of Cab and MgO, and various properties were measured as shown in Table 6.
また、試料ｒ！ｌＬ４．１５に水溶性塩の含有量が最大
であるＳｒ／Ｔｉ比１．０５．Ｌｉ Ｆ７．０ｍｏ １
％添加の組成も併せて記す。Also, sample r! Sr/Ti ratio 1.05. Li F7.0mo 1
The composition of % addition is also described.
（以下余白）
まず、第５．第６表について解説すると、試料Ｎｏ１〜
３．１１〜１３．１５は比較例である。これに対し、そ
の他の本発明にかかる試料Ｎｏ４〜１０．１４はＢａＯ
，Ｃａｂ、ＭｇＯの添加効果が得られるものである。こ
こで第３成分のＢａｄ。(Left below) First, Section 5. To explain Table 6, sample No. 1~
3.11 to 13.15 are comparative examples. On the other hand, other samples Nos. 4 to 10.14 according to the present invention have BaO
, Cab, and MgO can be added. Here, the third component is Bad.
Ｃａｂ、ＭｇＯの添加量を規定したのは、これらの添加
剤を添加すると、ＳｒＴｉＯ３中のＳｒと置換し、結晶
構造に歪みを生じ半導体化が促進され、結果として誘電
率が増加する効果が期待されるが、０．１ｍｏ１％未満
では、試料ｒ！１１〜３に示すように誘電率を増加する
効果がないためである。一方１．０ｍｏｌ％を超えると
試料嵐１１〜１３．１５に示すように半導体化及び粒成
長が抑制され誘電率、ｔａｎδ、焼結密度などの特性が
低下するためである。The addition amounts of Cab and MgO were specified because the addition of these additives replaces Sr in SrTiO3, distorts the crystal structure, promotes semiconductor formation, and is expected to have the effect of increasing the dielectric constant. However, at less than 0.1mol%, the sample r! This is because, as shown in 11 to 3, there is no effect of increasing the dielectric constant. On the other hand, if it exceeds 1.0 mol %, semiconductor formation and grain growth will be suppressed and properties such as dielectric constant, tan δ, and sintered density will deteriorate, as shown in Sample Arashi 11 to 13.15.
なお、本発明の実施例では、一部の組み合わせについて
示したが他の組み合わせでも同様の効果があることを確
認した。さらに、本発明の実施例では、Ｌｉ、Ｆの添加
剤としてＬｉＦを用いたが他のＬｉとＦ化合物を添加し
、複合反応させたＬｉＦでも同様の効果を得られること
は言うまでもない。そして、Ｓｒ過剰のＳｒＴｉＯ３を
作成するにあたりＳｒＣＯ３を添加したが、酸化物や水
酸化物などＳｒを含む各種塩類を用いても同様の効果を
得られることは言うまでもない。さらに、また第２成分
のＣｕ ＊ Ｃｏ ＊ Ｍ ｎ ＋第３成分のＢａ。In the examples of the present invention, some combinations were shown, but it was confirmed that other combinations had similar effects. Further, in the examples of the present invention, LiF was used as an additive for Li and F, but it goes without saying that the same effect can be obtained by adding other Li and F compounds and carrying out a complex reaction with LiF. Although SrCO3 was added to prepare SrTiO3 containing excess Sr, it goes without saying that similar effects can be obtained by using various salts containing Sr such as oxides and hydroxides. Furthermore, the second component Cu*Co*Mn+the third component Ba.
Ｃａ、Ｍｇの添加剤としてＣｕｂ、Ｃｏ２Ｏ３゜ＭｎＣ
Ｏ３，ＢａＯ，Ｃａｂ、ＭｇＯを用いたが、酸化物、炭
酸化物、水酸化物などＣｕ、Ｃ０．Ｍｎ。Cub, Co2O3゜MnC as additives for Ca and Mg
Although O3, BaO, Cab, and MgO were used, Cu, C0. Mn.
Ｂａ、Ｃａ、Ｍｇを含む各種塩類を用いても同様の効果
を得られることは言うまでもない。このようにして得ら
れた素子はバリスタ電圧が比較的低（、α、誘電率が大
きく、信頼性に優れているといった特性を同時に満足す
るため、ノイズや静電気の抑制に有効であり、誘電率が
大きいことから立ち上がりの鋭い急峻波パルスに対して
も優れた応答性を示す。It goes without saying that similar effects can be obtained by using various salts containing Ba, Ca, and Mg. The device obtained in this way simultaneously satisfies the characteristics of a relatively low varistor voltage (, α, high dielectric constant, and excellent reliability), so it is effective in suppressing noise and static electricity, and has a high dielectric constant. Because of its large value, it exhibits excellent response even to steep wave pulses with a sharp rise.
発明の効果
以上に示したように本発明によれば、バリスタ電圧が比
較的低（、α、誘電率が大きく、ｊａｎδが小さい、信
頼性に優れているといった特性を同時に満足することが
できる。Effects of the Invention As described above, according to the present invention, characteristics such as relatively low varistor voltage (, α, large dielectric constant, small jan δ, and excellent reliability) can be satisfied at the same time.
従来のＺｎＯ系バリスタに比べ、バリスタ電圧が比較的
低く、α、誘電率が大きいためノイズや静電気のといっ
た立ち上がりの鋭い急峻波パルスに対して極めて有効で
ある。Compared to conventional ZnO-based varistors, the varistor voltage is relatively low and α and dielectric constant are large, so it is extremely effective against steep wave pulses with a sharp rise such as noise and static electricity.
従って、本発明によればノイズ、静電気から半導体およ
び回路を保護することのできる素子を得ることができ、
その実用上の効果は極めて大きいものである。Therefore, according to the present invention, it is possible to obtain an element that can protect semiconductors and circuits from noise and static electricity.
Its practical effects are extremely large.
また、従来の５ｒＴｉＣｈ系バリスタの焼結温度１４０
０℃以上に比べ、本発明では１０００〜１４００℃の比
較的低温で焼結が可能となり焼結過程のエネルギー量の
削減が期待される。In addition, the sintering temperature of the conventional 5rTiCh varistor is 140
Compared to 0°C or higher, the present invention enables sintering at a relatively low temperature of 1000 to 1400°C, and is expected to reduce the amount of energy in the sintering process.
第１図は粒径と焼結密度の関係を示す特性図、第２図は
焼温度とＬｉ、Ｆの残存量の関係を示す特性図、第３匡
は本発明の実施例における電圧依存性非直線抵抗体磁器
を示す上面図、第４図は同素子の断面図、第５図は水溶
性塩の含量と容量変化率を関係を示す特性図である。
第
！
図
１・・・・・・焼結体、
２゜
３・・・・・・電極。Figure 1 is a characteristic diagram showing the relationship between grain size and sintered density, Figure 2 is a characteristic diagram showing the relationship between sintering temperature and residual amounts of Li and F, and the third box is the voltage dependence in the example of the present invention. FIG. 4 is a top view showing a non-linear resistor ceramic, FIG. 4 is a cross-sectional view of the same element, and FIG. 5 is a characteristic diagram showing the relationship between the content of water-soluble salt and the rate of change in capacity. No.! Figure 1: Sintered body, 2゜3: Electrode.
Claims (3)
Ｓｒを含有し、さらにＬｉとＦを合計で０．００７〜０
．５００ｗｔ％含有した ＳｒＴｉＯ＿３に、ＣｅＯ＿２，Ｙ＿２Ｏ＿３，Ｌａ＿
２Ｏ＿３のうち少なくとも一種類以上を０．１〜２．０
ｍｏｌ％とＳｉＯ＿２，ＣｕＯ，Ｃｏ＿２Ｏ＿３，Ｍｎ
ＣＯ＿３のうち少なくとも一種類以上を０．１〜２．０
ｍｏｌ％とＢａＯ，ＣａＯ，ＭｇＯのうち少なくとも一
種類以上を０．１〜１．０ｍｏｌ％含ませてなる電圧依
存性非直線抵抗体磁器。(1) Contains excess Sr so that the ratio of Sr and Ti is 1.001≦Sr/Ti≦1.05, and further contains Li and F in a total of 0.007 to 0.
．． CeO_2, Y_2O_3, La_
0.1 to 2.0 of at least one type of 2O_3
mol% and SiO_2, CuO, Co_2O_3, Mn
0.1 to 2.0 of at least one type of CO_3
A voltage-dependent nonlinear resistor ceramic containing 0.1 to 1.0 mol% of at least one of BaO, CaO, and MgO.
が０．０５０ｗｔ％以下であることを特徴とする特許請
求の範囲第１項に記載の電圧依存性非直線抵抗体磁器。(2) The voltage-dependent non-linear resistance ceramic according to claim 1, wherein the water-soluble salt contained in the voltage-dependent non-linear resistance ceramic is 0.050 wt% or less.
末を原料として１．００１≦Ｓｒ／Ｔｉ≦１．０５とな
るようにＳｒ化合物を添加し、さらに ＬｉＦ０．７〜７．０ｍｏｌ％とＣｅＯ＿２，Ｙ＿２Ｏ
＿３，Ｌａ＿２Ｏ＿３のうち少なくとも一種類以上を０
．１〜２．０ｍｏｌ％とＳｉＯ＿２，ＣｕＯ，Ｃｏ＿２
Ｏ＿３，ＭｎＣＯ＿３のうち少なくとも一種類以上を０
．１〜２．０ｍｏｌ％とＢａＯ，ＣａＯ，ＭｇＯのうち
少なくとも一種類以上を０．１〜１．０ｍｏｌ％を添加
した混合粉末を成形し、還元雰囲気中で１０００℃〜１
４００℃の温度で焼成し、その後、空気中で５００〜１
０００℃の熱処理後電極を設けるか、または、５００〜
９００℃で焼き付け可能な銀ペイントを焼き付けた磁器
に含まれる水溶性塩が０．０５０ｗｔ％以下であること
を特徴とする電圧依存性非直線抵抗体磁器の製造方法。(3) Using SrTiO_3 powder with an average particle size of 0.5 μm or less as a raw material, add an Sr compound so that 1.001≦Sr/Ti≦1.05, and further add LiF0.7 to 7.0 mol% and CeO_2 , Y_2O
At least one of _3, La_2O_3 is 0
．． 1 to 2.0 mol% and SiO_2, CuO, Co_2
At least one of O_3 and MnCO_3 is 0
．． 1 to 2.0 mol% and 0.1 to 1.0 mol% of at least one of BaO, CaO, and MgO was molded and heated at 1000°C to 1.0 mol% in a reducing atmosphere.
Calcinate at a temperature of 400℃, then heat in air at 500-1
Provide electrodes after heat treatment at 500°C or
A method for producing voltage-dependent nonlinear resistor porcelain, characterized in that water-soluble salts contained in the porcelain baked with silver paint that can be baked at 900° C. are 0.050 wt% or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1277424A JPH03138905A (en) | 1989-10-24 | 1989-10-24 | Voltage dependent non-linear ceramic resistor and its manufacture |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1277424A JPH03138905A (en) | 1989-10-24 | 1989-10-24 | Voltage dependent non-linear ceramic resistor and its manufacture |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03138905A true JPH03138905A (en) | 1991-06-13 |
Family
ID=17583367
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1277424A Pending JPH03138905A (en) | 1989-10-24 | 1989-10-24 | Voltage dependent non-linear ceramic resistor and its manufacture |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03138905A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100312605B1 (en) * | 1998-04-13 | 2001-11-03 | 무라타 야스타카 | Semiconducting ceramic and semiconducting ceramic electronic element |
| JPWO2008004389A1 (en) * | 2006-07-03 | 2009-12-03 | 株式会社村田製作所 | Multilayer semiconductor ceramic capacitor with varistor function and manufacturing method thereof |
| WO2012093575A1 (en) * | 2011-01-05 | 2012-07-12 | 株式会社 村田製作所 | Method of manufacturing stacked semiconductor ceramic capacitor and stacked semiconductor ceramic capacitor |
-
1989
- 1989-10-24 JP JP1277424A patent/JPH03138905A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100312605B1 (en) * | 1998-04-13 | 2001-11-03 | 무라타 야스타카 | Semiconducting ceramic and semiconducting ceramic electronic element |
| JPWO2008004389A1 (en) * | 2006-07-03 | 2009-12-03 | 株式会社村田製作所 | Multilayer semiconductor ceramic capacitor with varistor function and manufacturing method thereof |
| JP4666269B2 (en) * | 2006-07-03 | 2011-04-06 | 株式会社村田製作所 | Multilayer semiconductor ceramic capacitor with varistor function and manufacturing method thereof |
| WO2012093575A1 (en) * | 2011-01-05 | 2012-07-12 | 株式会社 村田製作所 | Method of manufacturing stacked semiconductor ceramic capacitor and stacked semiconductor ceramic capacitor |
| JP5418993B2 (en) * | 2011-01-05 | 2014-02-19 | 株式会社村田製作所 | Manufacturing method of multilayer semiconductor ceramic capacitor and multilayer semiconductor ceramic capacitor |
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