JPH0249308A - Highly dielectric porcelain compound - Google Patents
Highly dielectric porcelain compoundInfo
- Publication number
- JPH0249308A JPH0249308A JP63200626A JP20062688A JPH0249308A JP H0249308 A JPH0249308 A JP H0249308A JP 63200626 A JP63200626 A JP 63200626A JP 20062688 A JP20062688 A JP 20062688A JP H0249308 A JPH0249308 A JP H0249308A
- Authority
- JP
- Japan
- Prior art keywords
- dielectric constant
- exceeded
- dielectric factor
- main components
- high dielectric
- 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.)
- Granted
Links
- 229910052573 porcelain Inorganic materials 0.000 title claims abstract description 11
- 150000001875 compounds Chemical class 0.000 title abstract 2
- 239000000203 mixture Substances 0.000 claims description 22
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 abstract description 8
- 229910002113 barium titanate Inorganic materials 0.000 abstract 3
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 abstract 3
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 abstract 3
- 238000005245 sintering Methods 0.000 abstract 3
- NLQFUUYNQFMIJW-UHFFFAOYSA-N dysprosium(III) oxide Inorganic materials O=[Dy]O[Dy]=O NLQFUUYNQFMIJW-UHFFFAOYSA-N 0.000 abstract 2
- 239000000126 substance Substances 0.000 abstract 1
- 239000000919 ceramic Substances 0.000 description 12
- 239000013078 crystal Substances 0.000 description 7
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- 239000003990 capacitor Substances 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000032798 delamination Effects 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 239000003985 ceramic capacitor Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 229910015806 BaTiO2 Inorganic materials 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
Landscapes
- Compositions Of Oxide Ceramics (AREA)
- Inorganic Insulating Materials (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、磁器コンデンサ等に使用される高誘電率磁器
組成物に係り、特にＪＩＳのＦ特性を満たす積層磁器コ
ンデンサの製造に適する高誘電率磁器組成物に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a high dielectric constant ceramic composition used for ceramic capacitors, etc., and in particular to a high dielectric constant ceramic composition suitable for manufacturing a laminated ceramic capacitor that satisfies JIS F characteristics. The present invention relates to a porcelain composition.
ＪＩＳのＦ特性の規格は、誘電率の温度変化が、−２５
℃〜＋８５℃の温度範囲において、＋２０℃を基準温度
として、＋３０％〜−８０％以内であることを定めてい
る。The JIS F characteristic standard states that the temperature change in dielectric constant is -25
In the temperature range from .degree. C. to +85.degree. C., the temperature is defined to be within +30% to -80%, with +20.degree. C. as the reference temperature.
従来、このＦ特性用として実用化されている高誘電率磁
器組成物として、例えばＢａＴｉ０ｚ −ＢａＺｒ０３
−ＢａＳｎ０３−ＣａＴｉ０３系の組成物が存在する。Hitherto, examples of high permittivity ceramic compositions that have been put into practical use for this F characteristic include BaTi0z-BaZr03.
-BaSn03-CaTi03 type compositions exist.
しかし、この組成物を用いて積層コンデンサを形成した
場合、歩留まりが悪く、また、破壊電圧も低いという欠
点があった。However, when a multilayer capacitor is formed using this composition, there are disadvantages in that the yield is poor and the breakdown voltage is also low.
この原因は、高誘電率磁器の結晶粒径が１０〜２０μｍ
と大きいことにある。積層コンデンサは、磁器の薄層と
内部電極となる２０〜３０μｍ程の厚さの銀電極層とを
積層し、焼成して作成されるが、磁器の結晶粒径が銀電
極層の厚さ程度に大きい場合には、焼成中に磁器素地と
銀電極層との間にハガレが生ずる。これをデラミネーシ
ョンというが、このデラミネーションが歩留まりの悪化
および破壊電圧の低下をもたらしている。The reason for this is that the crystal grain size of high dielectric constant porcelain is 10 to 20 μm.
There is a big thing. A multilayer capacitor is created by laminating a thin layer of porcelain and a silver electrode layer with a thickness of about 20 to 30 μm, which serves as an internal electrode, and firing it, but the crystal grain size of the porcelain is about the thickness of the silver electrode layer. If the thickness is too large, peeling will occur between the porcelain base and the silver electrode layer during firing. This is called delamination, and this delamination causes a deterioration in yield and a decrease in breakdown voltage.
本発明は、ＪＩＳのＦ特性規格を満たすとともに、結晶
粒径が平均５μｍ以下となるよう組成を選定することに
より、従来品の持つ上記欠点を改善した、誘電率が８０
００〜１３０００程度の高誘電率磁器組成物を提供する
ことを目的としている。The present invention satisfies the JIS F characteristic standard and improves the above-mentioned drawbacks of conventional products by selecting a composition so that the average crystal grain size is 5 μm or less, and the dielectric constant is 80.
The purpose of the present invention is to provide a ceramic composition with a high dielectric constant of about 00 to 13,000.
本発明は上記課題を解決するため、
ＢａＴｉＯｓ ９７．０〜９８．２５ｍｏＪ％Ｎｂｚ
Ｏｓ ０．７５〜１．５０ ｍｏ４２％Ｄｙｚ○
ｙ ０．５０〜２．００ ｍｏ ｊ！％からなる
主成分に対して、主成分の０．２〜０．８ｗｔ％のＣｅ
Ｏ２を添加して高誘電率磁器組成物を得た。In order to solve the above problems, the present invention provides the following steps: BaTiOs 97.0-98.25moJ%Nbz
Os 0.75-1.50 mo42%Dyz○
y 0.50~2.00 mo j! % of the main component, 0.2 to 0.8 wt% of the main component is Ce
A high dielectric constant ceramic composition was obtained by adding O2.
また、上記高誘電率磁器組成物に、更に、主成分の０．
０１〜０，３ｗｔ％のＭｎＯを添加して高誘電率磁器組
成物を得た。In addition, the above-mentioned high dielectric constant ceramic composition may further contain 0.0% of the main component.
A high dielectric constant ceramic composition was obtained by adding 0.01 to 0.3 wt% of MnO.
そして、これらの組成範囲の高誘電率磁器組成物は、本
発明の目的とするＪＩＳのＦ特性を満たすとともに、結
晶粒径が微細化していることが判明した。It has also been found that high dielectric constant ceramic compositions having these composition ranges satisfy the JIS F characteristic, which is the object of the present invention, and have finer grain sizes.
本発明を実施例にもとづき詳細に説明する。 The present invention will be explained in detail based on examples.
出発原料としてＢａＣｏ：ｌ 、ＴｔＯｚ 、ＮｂｚＯ
ｓ、ＤＶｚＯｓ 、ＣＥ１０２及びＭｎＣＯ５を用いて
第１表に示す組成比になるように計量し、これをボット
ミルで混合、脱水、乾燥したのち、仮プレスし、１１０
０℃〜１２００℃で２時間仮焼成した。次いで、粉砕、
脱水、乾燥後、ポリビニルアルコールをバインダーとし
て加え顆粒にし、これを約３ｔＯｎ／ｃＩ１１２の成型
圧力でプレスし直径１６．５關φ、厚さ０．６ ｍの円
板状成型物を作成した。この成型体を空気中で１２８０
°Ｃ〜１３６０℃、２時間焼成し、得られた素体に銀電
極を焼き付けて試料を作成した。BaCo:l, TtOz, NbzO as starting materials
s, DVzOs, CE102, and MnCO5 were weighed to have the composition ratio shown in Table 1, mixed in a bot mill, dehydrated, dried, and temporarily pressed.
Preliminary firing was performed at 0°C to 1200°C for 2 hours. Then, crushing,
After dehydration and drying, polyvinyl alcohol was added as a binder to make granules, which were pressed at a molding pressure of about 3 tOn/cI112 to produce a disc-shaped molded product with a diameter of 16.5 mm and a thickness of 0.6 m. This molded body was heated to 1280°C in the air.
A sample was prepared by baking at 1360° C. for 2 hours and baking a silver electrode onto the obtained element body.
このようにして得た試料について、それぞれ電気特性を
測定した結果を第１表に示す。Table 1 shows the results of measuring the electrical properties of the samples thus obtained.
ここで、誘電率Ｅｓ及び誘電体損失ｔａｎδは室温２０
°Ｃ１周波数Ｉ ＫＨ２で測定した。また、誘電率の温
度変化率Ｔ−Ｃは、＋２０℃を基準として、２５°Ｃ〜
＋８５℃の誘電率の温度変化率（％）を求めた。Here, the dielectric constant Es and the dielectric loss tan δ are at room temperature 20
Measured at °C1 frequency I KH2. In addition, the temperature change rate T-C of the dielectric constant is from 25°C to +20°C.
The temperature change rate (%) of the dielectric constant at +85°C was determined.
第１表中試料番号１．２．５．８．１０．１３．１４．
１５．１９．２０．２４は本発明の組成範囲外のもので
あり、試料番号３．４．６．７．９．１１．１２．１６
．１７．１８．２２．２３は、本発明の組成範囲内のも
のである。Sample number 1.2.5.8.10.13.14 in Table 1.
15.19.20.24 is outside the composition range of the present invention, sample number 3.4.6.7.9.11.12.16
．． 17.18.22.23 are within the composition range of the present invention.
以下余白
本発明において組成範囲を比定した理由は次の通りであ
る。The reason for determining the composition range in the present invention is as follows.
ＢａＴｉＯ２が９７．０ｍｏ １２％未満では誘電率が
小さくなり、９８．２５ ｍｏｊ！％を超えると焼結性
が悪くなる。When BaTiO2 is less than 97.0 mo 12%, the dielectric constant becomes small and becomes 98.25 moj! If it exceeds %, sinterability will deteriorate.
同様に、Ｄ ｙｚ Ｏ３が０．５０ ｍｏｌ％未満では
、誘電体損失ｔａｎδが大きくなり焼結性も悪く、絶縁
抵抗も悪くなる。２．０ｍｏ！！％を超えると誘電率が
小さくなり温度８５℃における誘電率温度変化率が大き
くなる。Ｎｂ２Ｏ５が０．７５ ｍｏｂ％未満では焼結
性が悪＜ １．５０ ｍｏｌ％を超えると誘電率が小
さくなる。第１図は本発明の主成分の組成範囲を示して
いる。第１図において試料番号１４〜２４が図示されて
いないのは、三元図上は試料番号７と同一位置にある。Similarly, if D yz O3 is less than 0.50 mol %, the dielectric loss tan δ becomes large, the sinterability is poor, and the insulation resistance is also poor. 2.0mo! ! %, the dielectric constant decreases and the rate of change in dielectric constant with temperature at a temperature of 85° C. increases. If Nb2O5 is less than 0.75 mol%, the sinterability is poor; if it exceeds 1.50 mol%, the dielectric constant is low. FIG. 1 shows the composition range of the main components of the present invention. The reason why sample numbers 14 to 24 are not shown in FIG. 1 is that they are at the same position as sample number 7 on the ternary diagram.
また、ＣｅＯ，は、キュリーポイントを一側へ移動させ
る即ちシフターの役割をしている。添加量が主成分の０
．２ｗ ｔ％未満ではキュリーポイントが常温以上とな
り誘電体損失ｔａｎδが悪く、誘電率も小さい。Moreover, CeO moves the Curie point to one side, that is, plays the role of a shifter. Added amount is 0 of the main component
．． If it is less than 2wt%, the Curie point will be higher than room temperature, the dielectric loss tan δ will be poor, and the dielectric constant will be small.
一方、Ｑ、３ｗｔ％を超えるとキュリーポイントが常温
以下となり誘電率が低くなり誘電率温度変化率が温度＋
８５℃でＪＩＳのＦ特性規格をはずれる。On the other hand, when Q exceeds 3wt%, the Curie point becomes below room temperature, the dielectric constant decreases, and the temperature change rate of the dielectric constant increases
At 85°C, it exceeds the JIS F characteristic standard.
ＭｎＯの添加量が主成分の０．０１ｗｔ％未満では焼結
性が悪く、絶縁抵抗も低くなる。一方、０．３ｗｔ％を
超えると誘電率が低くなり実用的でなくなる。If the amount of MnO added is less than 0.01 wt% of the main component, sinterability will be poor and insulation resistance will also be low. On the other hand, if it exceeds 0.3 wt%, the dielectric constant becomes low and becomes impractical.
第２図は高誘電率磁器焼結体の表面の結晶構造を３００
０倍に拡大した顕微鏡写真であり、（Ａ）は従来品、（
Ｂ）は本発明のＢ ａ Ｔ ｉ Ｏ３Ｎ ｂ ｔＯｓ
ＤＶｚＯｓ Ｃｅ０ｚ −ＭｎＯ系高誘電率磁器を
示している。同図から明らかなように本発明に係る高誘
電率磁器の結晶粒径は平均５μｍ以下となっている。Figure 2 shows the crystal structure of the surface of a high dielectric constant porcelain sintered body.
These are micrographs magnified 0 times, (A) is the conventional product, (
B) is B a T i O3N b tOs of the present invention
DVzOs Ce0z -MnO-based high dielectric constant ceramic is shown. As is clear from the figure, the average crystal grain size of the high dielectric constant ceramic according to the present invention is 5 μm or less.
また、第１表から明らかなように、本発明の高誘電率磁
器組成物は、誘電率が約８０００〜１３０００、誘電率
温度変化率も一２５℃〜＋８５℃の温度範囲で、２０℃
を基準として＋３０％〜−８０％以内にある。Furthermore, as is clear from Table 1, the high dielectric constant ceramic composition of the present invention has a dielectric constant of about 8,000 to 13,000, and a temperature change rate of the dielectric constant of about 20°C in the temperature range of -25°C to +85°C.
It is within +30% to -80% based on .
本発明に係る高誘電率磁器組成物は誘電率が高く、誘電
率温度変化率もＪ Ｉ ＳのＦ特性を満足している。ま
た、積層コンデンサに応用した場合、結晶粒径の微細化
によりデラミネーションが防止でき、歩留まりの向上、
破壊電圧の上昇等が図れ、実用的価値が大きい。The high dielectric constant ceramic composition according to the present invention has a high dielectric constant, and the temperature change rate of the dielectric constant also satisfies the F characteristics of JIS. In addition, when applied to multilayer capacitors, delamination can be prevented by reducing the crystal grain size, improving yields and
It can increase breakdown voltage, etc., and has great practical value.
第１図は本発明に係る高誘電率磁器組成物の主成分を示
す三成分系図、第２図は焼結体の表面の結晶構造を示す
拡大写真であり、同図＜Ａ）は従来品、同図（Ｂ）は本
発明の磁器を示す。
特許出願人 ティーデイ−ケイ株式会社代理人弁理士
山 谷 晧 榮
ｂｚ ＯｓFigure 1 is a ternary component diagram showing the main components of the high dielectric constant porcelain composition according to the present invention, Figure 2 is an enlarged photograph showing the crystal structure of the surface of the sintered body, and <A) is the conventional product. , the same figure (B) shows the porcelain of the present invention. Patent applicant: TDC Co., Ltd., agent patent attorney
Akira Yamatani Sakae bz Os
Claims (1)
ｂ＿２Ｏ＿５０．７５〜１．５０ｍｏｌ％Ｄｙ＿２Ｏ＿
３０．５０〜２．００ｍｏｌ％からなる主成分に対して
、主成分の０．２〜０．８ｗｔ％のＣｅＯ＿２及び、主
成分の０．０１〜０．３ｗｔ％のＭｎＯを添加したこと
を特徴とする高誘電率磁器組成物。(1) BaTiO_397.0-98.25mol%N
b_2O_50.75-1.50mol%Dy_2O_
It is characterized by adding CeO_2 of 0.2 to 0.8 wt% of the main component and MnO of 0.01 to 0.3 wt% of the main component to the main component consisting of 30.50 to 2.00 mol%. High dielectric constant porcelain composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63200626A JP2654113B2 (en) | 1988-08-11 | 1988-08-11 | High dielectric constant porcelain composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63200626A JP2654113B2 (en) | 1988-08-11 | 1988-08-11 | High dielectric constant porcelain composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0249308A true JPH0249308A (en) | 1990-02-19 |
| JP2654113B2 JP2654113B2 (en) | 1997-09-17 |
Family
ID=16427507
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63200626A Expired - Lifetime JP2654113B2 (en) | 1988-08-11 | 1988-08-11 | High dielectric constant porcelain composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2654113B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05270905A (en) * | 1992-03-25 | 1993-10-19 | Taiyo Yuden Co Ltd | Porcelain condenser and its production |
| JPH05270907A (en) * | 1992-03-25 | 1993-10-19 | Taiyo Yuden Co Ltd | Porcelain condenser and its production |
| JPH05270906A (en) * | 1992-03-25 | 1993-10-19 | Taiyo Yuden Co Ltd | Porcelain condenser and its production |
| JPH05270904A (en) * | 1992-03-25 | 1993-10-19 | Taiyo Yuden Co Ltd | Porcelain condenser and its production |
-
1988
- 1988-08-11 JP JP63200626A patent/JP2654113B2/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05270905A (en) * | 1992-03-25 | 1993-10-19 | Taiyo Yuden Co Ltd | Porcelain condenser and its production |
| JPH05270907A (en) * | 1992-03-25 | 1993-10-19 | Taiyo Yuden Co Ltd | Porcelain condenser and its production |
| JPH05270906A (en) * | 1992-03-25 | 1993-10-19 | Taiyo Yuden Co Ltd | Porcelain condenser and its production |
| JPH05270904A (en) * | 1992-03-25 | 1993-10-19 | Taiyo Yuden Co Ltd | Porcelain condenser and its production |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2654113B2 (en) | 1997-09-17 |
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