JP2784864B2 - Dielectric porcelain and porcelain capacitor - Google Patents
Dielectric porcelain and porcelain capacitorInfo
- Publication number
- JP2784864B2 JP2784864B2 JP4276673A JP27667392A JP2784864B2 JP 2784864 B2 JP2784864 B2 JP 2784864B2 JP 4276673 A JP4276673 A JP 4276673A JP 27667392 A JP27667392 A JP 27667392A JP 2784864 B2 JP2784864 B2 JP 2784864B2
- Authority
- JP
- Japan
- Prior art keywords
- porcelain
- dielectric
- sample
- capacitor
- compound
- 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.)
- Expired - Lifetime
Links
- 229910052573 porcelain Inorganic materials 0.000 title claims description 32
- 239000003990 capacitor Substances 0.000 title description 10
- 239000003985 ceramic capacitor Substances 0.000 claims description 18
- 150000002123 erbium compounds Chemical class 0.000 claims description 8
- 150000002291 germanium compounds Chemical class 0.000 claims description 4
- 150000002697 manganese compounds Chemical class 0.000 claims description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 28
- 239000000919 ceramic Substances 0.000 description 22
- 239000000203 mixture Substances 0.000 description 11
- 238000010304 firing Methods 0.000 description 9
- 239000010936 titanium Substances 0.000 description 9
- 229910005793 GeO 2 Inorganic materials 0.000 description 8
- 239000011575 calcium Substances 0.000 description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 229910010293 ceramic material Inorganic materials 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000010410 layer Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229910052691 Erbium Inorganic materials 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 2
- VQCBHWLJZDBHOS-UHFFFAOYSA-N erbium(iii) oxide Chemical compound O=[Er]O[Er]=O VQCBHWLJZDBHOS-UHFFFAOYSA-N 0.000 description 2
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- FQNGWRSKYZLJDK-UHFFFAOYSA-N [Ca].[Ba] Chemical compound [Ca].[Ba] FQNGWRSKYZLJDK-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229940043430 calcium compound Drugs 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Ceramic Capacitors (AREA)
- Inorganic Insulating Materials (AREA)
Description
【0001】[0001]
【産業上の利用分野】本発明は、高い誘電率を有する誘
電体磁器及びこれを使用した単層又は積層の誘電体磁器
コンデンサに関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a dielectric ceramic having a high dielectric constant and a single-layer or multilayer dielectric ceramic capacitor using the same.
【0002】[0002]
【従来の技術】磁器コンデンサの誘電体磁器基体として
BaTiO3 (チタン酸バリウム)を主成分とした磁
器、又はBaTiO3 のBa(バリウム)の一部をCa
(カルシウム)に置換し、且つTi(チタン)の一部を
Zr(ジルコニウム)に置換した磁器を使用することは
公知である。また、これ等の磁器にMn(マンガン)の
化合物を含めることも公知である。この種の誘電体磁器
の比誘電率の最大値はほぼ14000である。BACKGROUND ART porcelain the BaTiO 3 as a dielectric ceramic substrate for magnetic capacitor (barium titanate) as a main component, or a portion of Ba (barium) of BaTiO 3 Ca
It is known to use a porcelain in which (calcium) is substituted and a part of Ti (titanium) is substituted by Zr (zirconium). It is also known to include Mn (manganese) compounds in these porcelains. The maximum value of the relative permittivity of this type of dielectric porcelain is approximately 14,000.
【0003】[0003]
【発明が解決しようとする課題】ところで、誘電体磁器
コンデンサの容量の増大及び信頼性の向上が要求されて
いる。容量の増大を図るためには一対の電極間に介在す
る誘電体磁器層の厚みを薄くすることが考えられる。し
かし、誘電体磁器層を薄くすると、一対の電極間の絶縁
耐圧が低下する。容量の増大を図るための別の方法とし
て、比誘電率が高く、且つ絶縁耐圧の高い誘電体磁器を
使用する方法がある。しかし、従来のBaTiO3 系の
誘電体磁器では比誘電率及び絶縁耐圧に限界があり、高
容量化に限界があった。また積層磁器コンデンサを形成
する際に、例えば1300℃以上のような高温で焼成す
る場合には内部電極の材料しして高価なパラジウム(P
d)を使用することが必要になり、必然的にコスト高に
なった。By the way, there is a demand for an increase in capacitance and an improvement in reliability of a dielectric ceramic capacitor. In order to increase the capacitance, it is conceivable to reduce the thickness of the dielectric ceramic layer interposed between the pair of electrodes. However, when the dielectric ceramic layer is made thin, the dielectric strength between the pair of electrodes decreases. As another method for increasing the capacitance, there is a method using a dielectric ceramic having a high relative dielectric constant and a high withstand voltage. However, the conventional BaTiO 3 -based dielectric porcelain has a limit in the relative dielectric constant and dielectric strength, and has a limit in increasing the capacity. When firing at a high temperature such as 1300 ° C. or more when forming a multilayer ceramic capacitor, expensive palladium (P
It became necessary to use d), which inevitably increased the cost.
【0004】そこで、本発明の目的は、−25℃〜+8
5℃の範囲における比誘電率の最大値が14000以上
であり、20℃のtan δ(誘電体損失)が1.5%以下
であり、150℃における抵抗率が5×106 MΩ・c
m以上であり、1200℃以下の焼成で得ることができ
る誘電体磁器及びこれを使用した磁器コンデンサを提供
することにある。[0004] Therefore, an object of the present invention is to provide a temperature range from -25 ° C to + 8 ° C.
The maximum value of the relative dielectric constant in the range of 5 ° C. is 14000 or more, the tan δ (dielectric loss) at 20 ° C. is 1.5% or less, and the resistivity at 150 ° C. is 5 × 10 6 MΩ · c.
It is an object of the present invention to provide a dielectric ceramic which can be obtained by firing at 1200 ° C. or less and a ceramic capacitor using the same.
【0005】[0005]
【課題を解決するための手段】上記目的を達成するため
の本発明は、 (Ba1-x Cax )(Ti1-y Zry )O3 ここで、xは0.01〜0.10の範囲の数値、yは
0.10〜0.24の範囲の数値、から成る100モル
部の基本成分と、0.1〜2.0モル部のエルビウム化
合物と、0.03〜0.30モル部のマンガン化合物
と、0.01〜0.50モル部のゲルマニウム化合物と
から成る誘電体磁器に係わるものである。なお、請求項
2に示すように、請求項1の誘電体磁器を磁器コンデン
サの誘電体磁器基体として使用することができる。The present invention Means for Solving the Problems] To achieve the above object, where (Ba 1-x Ca x) (Ti 1-y Zr y) O 3, x is 0.01 to 0.10 Where y is a number in the range of 0.10 to 0.24, 100 mole parts of the basic component, 0.1 to 2.0 mole parts of the erbium compound, and 0.03 to 0.30. The present invention relates to a dielectric porcelain comprising a molar part of a manganese compound and 0.01 to 0.50 molar parts of a germanium compound. As described in claim 2, the dielectric ceramic of claim 1 can be used as a dielectric ceramic base of a ceramic capacitor.
【0006】[0006]
【発明の作用及び効果】誘電体磁器を本発明で特定した
組成にすると、−25℃〜+85℃の範囲における最大
比誘電率εmax が14000以上、20℃のtan δが
1.5%以下、150℃における抵抗率ρが5×106
MΩ・cm以上になる。本発明の磁器に含まれているエ
ルビウム(Er)化合物は絶縁耐圧の向上及び比誘電率
の向上に寄与している。即ち、エルビウム化合物は誘電
体磁器を構成している結晶粒子の平均粒径を例えば5μ
m以下のように小さくする作用を有する。またエルビウ
ム化合物は結晶粒子の平均粒径の例えば10倍以上のよ
うな異常粒子の発生を抑制する作用を有する。小さい結
晶粒子から成る誘電体磁器は、大きな結晶粒子から成る
誘電体磁器よりも大きな絶縁耐圧を示す。この結晶粒子
の大小は特に積層型磁器コンデンサにおける一対の電極
間の誘電体磁器を薄くする時に問題になる。ゲルマニウ
ム化合物は、1200℃以下の低温で焼成を可能にす
る。焼成温度が1200℃以下の場合には、コンデンサ
の電極材料をAgとPdとの混合物にすることが可能に
なり、コストの低減を図ることができる。When the dielectric ceramic has the composition specified in the present invention, the maximum relative permittivity ε max in the range of −25 ° C. to + 85 ° C. is 14000 or more, and the tan δ at 20 ° C. is 1.5% or less. Ρ at 150 ° C. is 5 × 10 6
MΩ · cm or more. The erbium (Er) compound contained in the porcelain of the present invention contributes to the improvement of the dielectric strength and the relative dielectric constant. That is, the erbium compound reduces the average particle size of the crystal grains constituting the dielectric ceramic to, for example, 5 μm.
It has the effect of reducing the size to m or less. Further, the erbium compound has an action of suppressing the generation of abnormal particles having an average particle size of, for example, 10 times or more of the crystal particles. A dielectric porcelain composed of small crystal grains exhibits a higher dielectric strength than a dielectric porcelain composed of large crystal grains. The size of the crystal grains becomes a problem particularly when the dielectric ceramic between the pair of electrodes in the multilayer ceramic capacitor is made thin. The germanium compound enables firing at a low temperature of 1200 ° C. or less. When the firing temperature is 1200 ° C. or lower, the electrode material of the capacitor can be a mixture of Ag and Pd, and the cost can be reduced.
【0007】[0007]
【第1の実施例】次に、本発明の第1の実施例において
は、図1に示す誘電体磁器コンデンサ10を作製した。
この磁器コンデンサ10は、円板状の誘電体磁器基体1
2と、この一対の主面に設けられた一対の電極14、1
6とから成る。First Embodiment Next, in a first embodiment of the present invention, a dielectric ceramic capacitor 10 shown in FIG. 1 was manufactured.
This porcelain capacitor 10 is a disk-shaped dielectric porcelain base 1
2 and a pair of electrodes 14, 1 provided on the pair of main surfaces.
6.
【0008】図1の磁器基体12を形成するために、ま
ず、チタン酸ジルコン酸バリウム・カルシウム化合物と
して(Ba1-x Cax )(Ti1-y Zry )O3 と、エ
ルビウム化合物として酸化エルビウム(Er2 O3 )
と、マンガン化合物として酸化マンガン(MnO)とゲ
ルマニウムの化合物として酸化ゲルマニウム(Ge
O2)とを用意した。次に、(Ba1-x Cax )(Ti
1-y Zry )O3 におけるx及びyの値と、Er
2 O3 、MnO及びGeO2 のモル部とを表1に示すよ
うに変化させて23種類の試料のための23種類の誘電
体磁器材料を用意した。In order to form a ceramic substrate 12 of FIG. 1, first, as zirconate titanate barium calcium compound and (Ba 1-x Ca x) (Ti 1-y Zr y) O 3, oxides as erbium compound Erbium (Er 2 O 3 )
And manganese oxide (MnO) as a manganese compound and germanium oxide (Ge) as a compound of germanium
O 2 ). Next, (Ba 1-x Ca x ) (Ti
1-y Zr y) and the values of x and y in O 3, Er
23 kinds of dielectric ceramic materials for 23 kinds of samples were prepared by changing the molar parts of 2 O 3 , MnO and GeO 2 as shown in Table 1.
【0009】試料NO. 1の誘電体磁器材料に従うコンデ
ンサを作製する場合には、基本成分のモル比を示すxが
0.05、yが0.19であるので、次式を満足する基
本成分を用意した。 (Ba0.95 Ca0.05)(Ti0.81 Zr0.19)O3 なお、基本成分は、この各元素のモル比を満足するよう
にBaCO3 (炭酸バリウム)とCaCO3 (炭酸カル
シウム)とTiO2 とZrO2 とを混合し、これを仮焼
きすることによって得た。次に、100モル部(100
0.00g)の基本成分に対して0.30モル部(4.
85g)のEr2 O3 と0.10モル部(0.30g)
のMnOと0.30モル部(1.33g)のGeO2 と
を付加し、これをボールミルにて約15時間混合及び粉
砕し、しかる後150℃、3時間乾燥することによって
磁器材料の粉末を得た。次に、この磁器材料の粉末に有
機バインダを添加して攪拌したものを使用して直径10
mm、厚さ0.6mmの円板状成形体をプレス成形によ
って形成した。次に、この磁器材料の成形体を空気中1
200℃で2時間焼成して焼結体から成る図1に示した
誘電体磁器基体12を得た。次に、この磁器基体12の
一方及び両方の主面にフリットを含まない銀ペーストを
印刷法で塗布し、しかる後800℃で焼付けることによ
って一対の電極14、16を形成し、磁器コンデンサ1
0を完成させた。尚、焼成後の磁器基体12の組成は焼
成前の磁器材料の組成と実質的に同−である。In the case of manufacturing a capacitor based on the dielectric ceramic material of sample No. 1, x, which represents the molar ratio of the basic components, is 0.05 and y is 0.19. Was prepared. (Ba 0.95 Ca 0.05 ) (Ti 0.81 Zr 0.19 ) O 3 The basic components are BaCO 3 (barium carbonate), CaCO 3 (calcium carbonate), TiO 2 and ZrO 2 so as to satisfy the molar ratio of each element. And calcined. Next, 100 mole parts (100
0.30 mol part (4.
85 g) of Er 2 O 3 and 0.10 mol part (0.30 g)
Of MnO and 0.30 mol part (1.33 g) of GeO 2 were added, mixed and ground in a ball mill for about 15 hours, and then dried at 150 ° C. for 3 hours to obtain a powder of the porcelain material. Obtained. Then, an organic binder was added to the powder of the porcelain material, and the mixture was stirred.
A disc-shaped compact having a thickness of 0.6 mm and a thickness of 0.6 mm was formed by press molding. Next, the molded body of the porcelain material was
It was fired at 200 ° C. for 2 hours to obtain a dielectric ceramic substrate 12 shown in FIG. 1 made of a sintered body. Next, a frit-free silver paste is applied to one and both main surfaces of the porcelain substrate 12 by a printing method, and then baked at 800 ° C. to form a pair of electrodes 14 and 16, thereby forming the porcelain capacitor 1.
0 was completed. The composition of the porcelain base 12 after firing is substantially the same as the composition of the porcelain material before firing.
【0010】次に、完成した磁器コンデンサの最大比誘
電率εmax とtan δと抵抗率ρと磁を次の要領で測定し
た。 (a) 最大比誘電率 磁器コンデンサを恒温槽に入れて−25℃から+85℃
まで温度を変化させた時の最大容量をインピーダンスア
ナライザで測定し、この最大容量と磁器基体との寸法に
基づいて比誘電率を計算した。 (b) tan δ(誘電体損失) 20℃におけるtan δを測定した。 (c) 抵抗率ρ 磁器コンデンサを150℃にして一対の電極14、16
間に直流100Vを20秒間印加して絶縁抵抗を測定
し、この絶縁抵抗の値と磁器基体12の寸法とから抵抗
率ρを計算した。Next, the maximum relative permittivity ε max , tan δ, resistivity ρ and magnetism of the completed ceramic capacitor were measured in the following manner. (A) Maximum relative permittivity Put a porcelain capacitor in a thermostat and keep it at -25 ° C to + 85 ° C.
The maximum capacitance when the temperature was changed until was measured by an impedance analyzer, and the relative permittivity was calculated based on the maximum capacitance and the dimensions of the porcelain base. (B) tan δ (dielectric loss) tan δ at 20 ° C. was measured. (C) Resistivity ρ The ceramic capacitor is set to 150 ° C.
During that time, 100 V DC was applied for 20 seconds to measure the insulation resistance, and the resistivity ρ was calculated from the value of the insulation resistance and the dimensions of the porcelain base 12.
【0011】試料NO. 1の場合には、表1に示すよう
に、εmax は19000、tan δは0.52%、ρは
9.0×106 MΩ・cmであった。In the case of Sample No. 1, as shown in Table 1, ε max was 19000, tan δ was 0.52%, and ρ was 9.0 × 10 6 MΩ · cm.
【0012】試料NO. 2〜23においても試料NO. 1と
同様な方法で磁器コンデンサを作り、同様な方法でε
max 、tan δ、ρを測定した。In each of the samples Nos. 2 to 23, a porcelain capacitor was formed in the same manner as in the case of the sample No. 1, and ε was formed in the same manner.
The max , tan δ, and ρ were measured.
【0013】[0013]
【表1】 [Table 1]
【0014】表1から明らかなように、本発明で特定し
た組成を満足する試料NO. 1、2、5、8、10、1
4、16、18〜23の磁器コンデンサは、本発明で目
標としている−25℃〜+85℃の範囲における最大比
誘電率εmax が14000以上、20℃のtan δが1.
5%以下、150℃における抵抗率ρが5×106 MΩ
・cm以上、1200℃以下での焼成を満足している。
表1の試料NO. 3、4、6、7、9、11、12、1
3、15、17の磁器コンデンサは本発明で目標とする
特性を得ることができないので、本発明以外のものであ
る。As is clear from Table 1, Samples No. 1, 2, 5, 8, 10, 1 satisfying the composition specified in the present invention.
The ceramic capacitors of 4, 16, and 18 to 23 have a maximum relative dielectric constant ε max in the range of −25 ° C. to + 85 ° C. which is the target of the present invention and a tan δ at 20 ° C.
5% or less, the resistivity ρ at 150 ° C. is 5 × 10 6 MΩ
Satisfies firing at a temperature of not less than cm and not more than 1200 ° C.
Sample Nos. 3, 4, 6, 7, 9, 11, 12, 1 in Table 1
The 3, 15, and 17 porcelain capacitors are other than the present invention because the characteristics desired by the present invention cannot be obtained.
【0015】誘電体磁器の組成の限定理由を次に述べ
る。xの値が0の場合は、試料NO. 3に示すようにε
max が所望値未満である。しかし、試料NO. 16に示す
ようにxの値が0.01になると、所望特性が得られ
る。従って、xの下限は0.01である。試料NO. 4に
示すように、xの値が0.12になると、εmax が所望
値未満になる。しかし、試料NO. 5及び16に示すよう
にxの値が0.10の場合には所望特性が得られる。従
って、xの上限は0.10である。The reasons for limiting the composition of the dielectric ceramic will now be described. When the value of x is 0, as shown in sample No. 3, ε
max is less than the desired value. However, when the value of x becomes 0.01 as shown in Sample No. 16, desired characteristics are obtained. Therefore, the lower limit of x is 0.01. As shown in sample No. 4, when the value of x becomes 0.12, ε max becomes less than the desired value. However, when the value of x is 0.10 as shown in Sample Nos. 5 and 16, desired characteristics can be obtained. Therefore, the upper limit of x is 0.10.
【0016】試料NO. 6に示すようにyの値が0.08
の場合にはεmax が所望値未満となり、且つtan δが所
望範囲よりも大きくなる。しかし、試料NO. 2に示すよ
うにyの値が0.10になると所望の特性が得られる。
従って、yの下限は0.10である。試料NO. 7に示す
ようにyの値が0.25の場合には、εmax が所望値未
満となる。しかし、試料NO. 8に示すようにyが0.2
4になると所望特性が得られる。従って、yの上限は
0.24である。As shown in sample No. 6, the value of y was 0.08
In this case, ε max is smaller than the desired value, and tan δ is larger than the desired range. However, when the value of y is 0.10 as shown in sample No. 2, desired characteristics are obtained.
Therefore, the lower limit of y is 0.10. When the value of y is 0.25 as shown in sample No. 7, ε max is less than the desired value. However, as shown in sample No. 8, y was 0.2
At 4, the desired characteristics are obtained. Therefore, the upper limit of y is 0.24.
【0017】試料NO. 9に示すようにEr2 O3 が0の
場合には抵抗率ρが所望値未満になる。しかし、試料N
O. 10に示すようにEr2 O3 を0.10モル部含め
ると、所望の特性を得ることができる。従って、Er2
O3 の下限は0.10モル部である。試料NO. 11に示
すようにEr2 O3 が2.10モル部の場合にはεmax
が所望値未満になる。しかし、試料NO. 2に示すように
Er2 O3 が2.00モル部の場合には所望の特性を得
ることができる。従って、Er2 O3 の上限は2.00
モル部である。As shown in Sample No. 9, when Er 2 O 3 is 0, the resistivity ρ becomes smaller than a desired value. However, sample N
As shown in O. 10, when 0.10 mol part of Er 2 O 3 is included, desired characteristics can be obtained. Therefore, Er 2
The lower limit of O 3 is 0.10 mol part. As shown in Sample No. 11, when Er 2 O 3 was 2.10 mol parts, ε max
Is less than the desired value. However, when Er 2 O 3 is 2.00 mol parts as shown in Sample No. 2 , desired characteristics can be obtained. Therefore, the upper limit of Er 2 O 3 is 2.00.
It is a molar part.
【0018】試料NO. 12に示すようにMnOが0.0
2モル部の場合にはρが所望値未満である。しかし、試
料NO. 2に示すようにMnOが0.03モル部の場合に
は所望の特性が得られる。従って、MnOの下限は0.
03モル部である。試料NO.13に示すようにMnOが
0.32の場合にはεmax 及びρが所望値未満である。
しかし、試料NO. 14に示すようにMnOが0.30モ
ル部の場合には、所望の特性が得られる。従って、Mn
Oの上限は0.30モル部である。As shown in sample No. 12, MnO was 0.0
In the case of 2 mole parts, ρ is less than the desired value. However, when MnO is 0.03 mol part as shown in Sample No. 2, desired characteristics can be obtained. Therefore, the lower limit of MnO is 0.1.
03 mol parts. As shown in sample No. 13, when MnO is 0.32, ε max and ρ are less than desired values.
However, as shown in Sample No. 14, when MnO is 0.30 mol part, desired characteristics can be obtained. Therefore, Mn
The upper limit of O is 0.30 mol part.
【0019】試料NO. 15に示すようにGeO2 が0の
場合には1200℃で焼結しない。しかし、試料NO.1
6に示すようにGeO2 が0.01モル部の場合には1
200℃で焼成が可能になる。従って、GeO2 の下限
は0.01モル部である。試料NO. 17に示すようにG
eO2 が0.5の場合にはεmax が所望値未満になる。
しかし、試料NO. 18に示すようにGeO2 が0.50
モル部の場合は所望の特性が得られる。従ってGeO2
の上限は0.50モル部である。As shown in Sample No. 15, when GeO 2 is 0, no sintering is performed at 1200 ° C. However, sample NO. 1
As shown in FIG. 6, when GeO 2 is 0.01 mol part, 1
Firing at 200 ° C. becomes possible. Therefore, the lower limit of GeO 2 is 0.01 mol part. As shown in Sample No. 17, G
When eO 2 is 0.5, ε max becomes less than the desired value.
However, as shown in Sample No. 18, GeO 2 was 0.50
In the case of the molar part, desired characteristics can be obtained. Therefore, GeO 2
Is an upper limit of 0.50 mol part.
【0020】[0020]
【第2の実施例】図2は第2の実施例の積層型磁器コン
デンサ18を示す。この磁器コンデンサ18は誘電体磁
器基体20と、複数の第1の内部電極22と、複数の第
2の内部電極24と、第1及び第2の外部電極26、2
8とから成る。誘電体磁器基体20は、図1の誘電体磁
器基体12と同様に、 (Ba1-x Cax )(Ti1-y Zry )O3 から成る100モル部の基本成分と、0.1〜2.0モ
ル部のエルビウム酸化物と、0.03〜0.30モル部
のマンガン酸化物と、0.01〜0.50モル部のゲル
マニウム酸化物とから成る組成物で形成されている。第
1及び第2の内部電極22、24は誘電体磁器基体20
にそれぞれ埋設され、これ等の一端が誘電体磁器基体2
0の一対の側面に露出し、ここに設けられた第1及び第
2の外部電極26、28に接続されている。第1及び第
2の内部電極22、24は誘電体磁器基体20の一部か
ら成る誘電体磁器層を介して互いに対向しているので、
これ等の間に容量を得ることができる。FIG. 2 shows a laminated ceramic capacitor 18 according to a second embodiment. The ceramic capacitor 18 includes a dielectric ceramic base 20, a plurality of first internal electrodes 22, a plurality of second internal electrodes 24, first and second external electrodes 26,
8 The dielectric ceramic body 20, similarly to the dielectric ceramic substrate 12 of FIG. 1, the basic components of 100 molar parts consisting of (Ba 1-x Ca x) (Ti 1-y Zr y) O 3, 0.1 It is formed of a composition consisting of 2.02.0 mol parts of erbium oxide, 0.03-0.30 mol parts of manganese oxide, and 0.01-0.50 mol parts of germanium oxide. . The first and second internal electrodes 22 and 24 are provided on the dielectric ceramic base 20.
And one end of each of them is buried in the dielectric ceramic base 2.
0, and are connected to the first and second external electrodes 26 and 28 provided here. Since the first and second internal electrodes 22 and 24 are opposed to each other via a dielectric ceramic layer that is a part of the dielectric ceramic base 20,
Between these, capacity can be obtained.
【0021】積層型磁器コンデンサを製造する時には、
周知のように、誘電体磁器材料から成るグリーンシート
(未焼成セラミックシート)を複数枚用意する。次に複
数のグリーンシートに第1及び第2の内部電極22、2
4を得るためのAg(銀)とPd(パラジウム)との混
合物を導電材料とする導電ペーストを所望パターンに塗
布して積層し、更にこの上下に導電ペーストを重ね、こ
れ等を圧着した後に、所望形状にカッテングして焼成す
る。これにより、図2に示す第1及び第2の内部電極2
2、24を伴なった磁器基体20が得られる。しかる
後、磁器基体20の側面に導電ペースト(Agペ−ス
ト)を塗布して焼付けることによって第1及び第2の外
部電極26、28を形成する。When manufacturing a laminated ceramic capacitor,
As is well known, a plurality of green sheets (unfired ceramic sheets) made of a dielectric ceramic material are prepared. Next, the first and second internal electrodes 22 and 2 are provided on the plurality of green sheets.
A conductive paste using a mixture of Ag (silver) and Pd (palladium) as a conductive material to obtain 4 is applied to a desired pattern and laminated, and furthermore, a conductive paste is layered on top and bottom of this, and these are pressed and bonded. Cut into the desired shape and fire. Thereby, the first and second internal electrodes 2 shown in FIG.
A porcelain base 20 with 2, 24 is obtained. Thereafter, the first and second external electrodes 26 and 28 are formed by applying and baking a conductive paste (Ag paste) to the side surface of the porcelain base 20.
【0022】図2の積層コンデンサ18についても、図
1の磁器コンデンサ10と同様に表1の試料NO. 1、
2、5、8、10、14、16、18〜23と同一の組
成の種々の試料を作成し、これ等のεmax 、tan δ、ρ
を測定したところ、本発明の目標特性を満足していた。As for the multilayer capacitor 18 of FIG. 2, the sample Nos. 1 and 2 of Table 1 are similar to the ceramic capacitor 10 of FIG.
Various samples having the same composition as 2, 5, 8, 10, 14, 16, 18 to 23 were prepared, and their ε max , tan δ, ρ
Was found to satisfy the target characteristics of the present invention.
【0023】[0023]
【変形例】本発明は上述の実施例に限定されるものでな
く、例えば次の変形が可能なものである。 (1) 基本成分(Ba1-x Cax )(Ti1-y Z
ry )O3 を得るために、BaTiO3 とCaZrO3
とを適当な比率で配合すること、又はBa(Ti1-y Z
ry )O3 とCaTiO3 とを適当な比率で配合するこ
と、又はBaTiO3 とCaTiO3 とBaZrO3 と
を適当な比率で配合することができる。 (2) 焼成温度は例えば1000〜1200℃の範囲
で変えることができる。 (3) 誘電体磁器材料の出
発物質として、Er2 O3 の代りにEr(OH)3 等の
エルビウム化合物を使用することができる。なお、本発
明の磁器を得る時はエルビウム化合物をEr2 O3 に換
算して0.1〜2.0モル部の範囲で含める。 (4) 誘電体磁器材料の出発物質としてMnOの代り
に、Mn3 O4 、Mn2 O3 、MnO2 等の酸化物、M
n(OH)2 、MnO(OH)等の水酸化物を使用する
ことができる。 (5) 基本成分を得るための仮焼工程を省いて、例え
ばBaTiO3 と、CaZrO3 と、Er2 O3 と、M
nOと、GeO2 を混合し、この混合物の成形体を作っ
て焼成してもよい。[Modifications] The present invention is not limited to the above-described embodiment, and for example, the following modifications are possible. (1) Basic component (Ba 1-x Ca x) (Ti 1-y Z
To obtain r y) O 3, BaT i O 3 and CaZrO 3
And Ba (Ti 1-y Z)
r y ) O 3 and CaTiO 3 can be blended at an appropriate ratio, or BaTiO 3 , CaTiO 3 and BaZrO 3 can be blended at an appropriate ratio. (2) The firing temperature can be changed, for example, in the range of 1000 to 1200 ° C. (3) An erbium compound such as Er (OH) 3 can be used instead of Er 2 O 3 as a starting material of the dielectric ceramic material. Incidentally, when obtaining the porcelain of the present invention contain in the range of 0.1 to 2.0 molar parts in terms of the erbium compound in the Er 2 O 3. (4) Instead of MnO, oxides such as Mn 3 O 4 , Mn 2 O 3 , MnO 2 , M
Hydroxides such as n (OH) 2 and MnO (OH) can be used. (5) The calcination step for obtaining the basic components is omitted, and for example, BaTiO 3 , CaZrO 3 , Er 2 O 3 , M
nO and GeO 2 may be mixed, and a molded body of this mixture may be prepared and fired.
【図1】第1の実施例の磁器コンデンサを示す正面図で
ある。FIG. 1 is a front view showing a ceramic capacitor according to a first embodiment.
【図2】第2の実施例の積層磁器コンデンサを示す断面
図である。FIG. 2 is a sectional view showing a laminated ceramic capacitor according to a second embodiment.
12 誘電体磁器基体 14、16 電極 12 Dielectric porcelain base 14, 16 Electrodes
───────────────────────────────────────────────────── フロントページの続き (72)発明者 堀江 克之 東京都台東区上野6丁目16番20号 太陽 誘電株式会社内 (58)調査した分野(Int.Cl.6,DB名) H01G 4/12 H01B 3/12──────────────────────────────────────────────────続 き Continued on the front page (72) Katsuyuki Horie, Inventor Taiyo Yuden Co., Ltd. 6-16-20 Ueno, Taito-ku, Tokyo (58) Field surveyed (Int.Cl. 6 , DB name) H01G 4/12 H01B 3/12
Claims (2)
モル部の基本成分と、 0.1〜2.0モル部のエルビウム化合物と、 0.03〜0.30モル部のマンガン化合物と、 0.01〜0.50モル部のゲルマニウム化合物とから
成る誘電体磁器。[Claim 1] (Ba 1-x Ca x) (Ti 1-y Zr y) O 3 wherein, x represents a number in the range from 0.01 to 0.10, y is the 0.10 to 0.24 A number in the range, consisting of 100
It consists of a molar part of a basic component, 0.1 to 2.0 parts by mole of an erbium compound, 0.03 to 0.30 part by mole of a manganese compound, and 0.01 to 0.50 part by mole of a germanium compound. Dielectric porcelain.
接触している少なくとも2つの電極とから成る磁器コン
デンサであって、前記誘電体磁器基体が、 (Ba1-x Cax )(Ti1-y Zry )O3 ここで、xは0.01〜0.10の範囲の数値、 yは0.10〜0.24の範囲の数値、から成る100
モル部の基本成分と、 0.1〜2.0モル部のエルビウム化合物と、 0.03〜0.30モル部のマンガン化合物と、 0.01〜0.50モル部のゲルマニウム化合物とから
成ることを特徴とする誘電体磁器コンデンサ。2. A ceramic capacitor comprising a dielectric porcelain base and at least two electrodes in contact with said dielectric porcelain base, wherein said dielectric porcelain base comprises: (Ba 1 -x Ca x ) (Ti here 1-y Zr y) O 3 , x is a number in the range from 0.01 to 0.10, y consists of numbers, in the range of from 0.10 to 0.24 100
It consists of a molar part of a basic component, 0.1 to 2.0 parts by mole of an erbium compound, 0.03 to 0.30 part by mole of a manganese compound, and 0.01 to 0.50 part by mole of a germanium compound. A dielectric ceramic capacitor characterized by the above-mentioned.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP4276673A JP2784864B2 (en) | 1992-09-21 | 1992-09-21 | Dielectric porcelain and porcelain capacitor |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP4276673A JP2784864B2 (en) | 1992-09-21 | 1992-09-21 | Dielectric porcelain and porcelain capacitor |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH06104138A JPH06104138A (en) | 1994-04-15 |
JP2784864B2 true JP2784864B2 (en) | 1998-08-06 |
Family
ID=17572725
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP4276673A Expired - Lifetime JP2784864B2 (en) | 1992-09-21 | 1992-09-21 | Dielectric porcelain and porcelain capacitor |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP2784864B2 (en) |
-
1992
- 1992-09-21 JP JP4276673A patent/JP2784864B2/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
JPH06104138A (en) | 1994-04-15 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP3046436B2 (en) | Ceramic capacitors | |
US5296425A (en) | Ceramic materials of improved dielectric constants, and capacitors fabricated therefrom | |
US20130083450A1 (en) | Dielectric composition and ceramic electronic component including the same | |
KR101983171B1 (en) | Dielectric ceramic composition and multilayer ceramic capacitor comprising the same | |
JP6870803B2 (en) | Dielectric porcelain composition and multilayer ceramic capacitors containing it | |
KR20190116112A (en) | Dielectric ceramic composition and multilayer ceramic capacitor comprising the same | |
KR20170081979A (en) | Dielectric ceramic composition and multilayer ceramic capacitor comprising the same | |
JP2872838B2 (en) | Multilayer ceramic capacitor and method of manufacturing the same | |
JPH0785460B2 (en) | Multilayer porcelain capacitor | |
JP2915217B2 (en) | Dielectric porcelain and porcelain capacitor | |
KR20170078064A (en) | Dielectric composition and multilayer ceramic capacitor comprising the same | |
JP2779740B2 (en) | Dielectric porcelain and porcelain capacitor | |
JP2784864B2 (en) | Dielectric porcelain and porcelain capacitor | |
JP2875936B2 (en) | Dielectric porcelain and porcelain capacitor | |
JP2001278659A (en) | Dielectric ceramics composition and manufacturing method for ceramic capacitor using it | |
KR20160092365A (en) | Dielectric ceramic composition, dielectric material and multilayer ceramic capacitor comprising the same | |
JP2872513B2 (en) | Dielectric porcelain and porcelain capacitor | |
JP2872502B2 (en) | Dielectric porcelain capacitors | |
JP2821768B2 (en) | Multilayer ceramic capacitors | |
JP3361531B2 (en) | Dielectric ceramic composition for Ni internal electrode | |
JP2872512B2 (en) | Dielectric porcelain and porcelain capacitor | |
KR20170017285A (en) | Dielectric ceramic composition and multilayer ceramic capacitor comprising the same | |
JPH0453042B2 (en) | ||
JP2719594B2 (en) | High dielectric constant porcelain composition | |
JPH06251622A (en) | Dielectric ceramic and ceramic capacitor |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 19980421 |