JPS6316504A - Ceramic forming composition and semiconductor ceramic substrate, dielectric ceramic substrate and capacitor using the same - Google Patents
Ceramic forming composition and semiconductor ceramic substrate, dielectric ceramic substrate and capacitor using the sameInfo
- Publication number
- JPS6316504A JPS6316504A JP61158466A JP15846686A JPS6316504A JP S6316504 A JPS6316504 A JP S6316504A JP 61158466 A JP61158466 A JP 61158466A JP 15846686 A JP15846686 A JP 15846686A JP S6316504 A JPS6316504 A JP S6316504A
- Authority
- JP
- Japan
- Prior art keywords
- ceramic
- forming composition
- mol
- dielectric
- mole
- 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
- 239000000919 ceramic Substances 0.000 title claims description 65
- 239000000203 mixture Substances 0.000 title claims description 36
- 239000004065 semiconductor Substances 0.000 title claims description 28
- 239000000758 substrate Substances 0.000 title claims description 20
- 239000003990 capacitor Substances 0.000 title claims description 17
- 229910052573 porcelain Inorganic materials 0.000 claims description 19
- 239000004020 conductor Substances 0.000 claims 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 19
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 12
- 230000007423 decrease Effects 0.000 description 9
- 239000000654 additive Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 230000000996 additive effect Effects 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000009413 insulation Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 238000010304 firing Methods 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 229910002113 barium titanate Inorganic materials 0.000 description 2
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical group [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】
［発明の利用分野］
本発明はセラミック形成組成物及びこれを用いた半導体
磁器基体、誘電体磁器基体並びにコンデンサーに関する
。DETAILED DESCRIPTION OF THE INVENTION [Field of Application of the Invention] The present invention relates to a ceramic forming composition, a semiconductor ceramic substrate, a dielectric ceramic substrate, and a capacitor using the same.
［従来の技術］
結晶粒界に絶縁層を形成した半導体磁器は、一般に大き
な誘電率を有する。この様な半導体磁器を用いて大きな
容量を有するコンデンサーを構成し得ることが知られて
いる。従来、この種の半導体磁器としては、チタン酸バ
リウムを主体成分とする磁器が多用されていた。このも
のは、誘電率が２０．０００と大きいものの、誘電損失
（ｔａｎδ）が５〜６％（１ｋＨｚ ）と大きく、また
、誘電率の温度変化も＋２０℃を基準として一２５〜＋
８５℃の範囲で±５０％と大きいものである。[Prior Art] Semiconductor ceramics in which an insulating layer is formed at grain boundaries generally have a large dielectric constant. It is known that a capacitor having a large capacity can be constructed using such semiconductor ceramics. Conventionally, as this type of semiconductor porcelain, porcelain whose main component is barium titanate has been frequently used. Although this material has a large dielectric constant of 20.000, the dielectric loss (tan δ) is large at 5 to 6% (1 kHz), and the temperature change in the dielectric constant is -25 to +25°C with reference to +20°C.
It is as large as ±50% in the range of 85°C.
一方、チタン酸バリウムのｔａｎａＡ■電率の温度変化
を改良する磁器としてチタン酸ス）Ｃ７ンチウムを主体
成分とする磁器が知られており、例えば特開昭５４−７
８４９８号に記載されている。On the other hand, porcelain whose main component is titanium titanate is known as a porcelain that improves the temperature change in the electric conductivity of barium titanate.
No. 8498.
又、ＴｉＯ２５１，５０モル％及びＳｒＯ４８．５０モ
ル％から成る主成分にＴａを添加せしめた磁器は、ｔａ
ｎ δが０．６％、−２５〜＋８５℃の誘電率の温度変
化が１０％以内と良好であるが、誘電率が３０゜０００
程度と低い。In addition, porcelain in which Ta is added to the main components consisting of 51.50 mol% of TiO2 and 48.50 mol% of SrO is
n δ is 0.6%, and the temperature change in dielectric constant from -25 to +85°C is within 10%, which is good, but the dielectric constant is 30°000
The degree is low.
また、例えばＴｉ０２及びＳｒＯから成る主成分にＮｂ
を添加せしめた磁器は、誘電率が５０．０００以上でｔ
ａｎδも１％以下と良好であるが、誘電率の温度変化が
一２５〜＋８５℃の範囲で±１３％を越える値となる。In addition, for example, Nb is added to the main component consisting of Ti02 and SrO.
Porcelain doped with
An δ is also good at 1% or less, but the temperature change in dielectric constant exceeds ±13% in the range of -25 to +85°C.
［発明の解決すべき問題点］
本発明は、前記従来の問題点を解決し、誘電率が大きく
、且つ温度特性が良好であり、誘電損失の小さなコンデ
ンサーを構成することのできるでラミック形成組成物、
及びこれを用いた半導体磁器基体と誘電体磁器基体並び
にコンデンサーを提供すべくなされたものである。[Problems to be Solved by the Invention] The present invention solves the above-mentioned conventional problems and provides a ramic-forming composition that has a large dielectric constant, good temperature characteristics, and can constitute a capacitor with small dielectric loss. thing,
The present invention has also been made to provide semiconductor ceramic substrates, dielectric ceramic substrates, and capacitors using the same.
［問題点を解決するための手段］
本発明によって提供されるセラミック形成組成物（以下
１本発明のセラミック形膚組成物という）は、ＴｉＯ２
５０，２０〜５３．５０モル％及び ５ｒ０４９．８０
〜４８．５０モル％から成る主成分ｉｏｏモル部に対し
、 ＭｎＯ２ ３．０〜５．０モル部、並びにＷＯ。[Means for Solving the Problems] The ceramic forming composition provided by the present invention (hereinafter referred to as the ceramic skin composition of the present invention) is composed of TiO2
50,20-53.50 mol% and 5r049.80
-48.50 mol % of the main component ioo mol parts: 3.0-5.0 mol parts MnO2 and WO.
０．０５〜０．３０モル部が含有されていることを特徴
とするものである。It is characterized by containing 0.05 to 0.30 mole parts.
本発明によって提供される半導体磁器基体（以下、本発
明の半導体磁器基体という）は、本発明のセラミック形
成組成物の焼成体から成ることを特徴とするものである
。The semiconductor ceramic substrate provided by the present invention (hereinafter referred to as the semiconductor ceramic substrate of the present invention) is characterized by being composed of a fired body of the ceramic forming composition of the present invention.
本発明によって提供される誘電体磁器基体（以下１本発
明の誘電体磁器基体という）は、本発明のセラミック形
成組成物の焼成体から成る半導体磁器の結晶粒界に絶縁
層が存在していることを特徴とするものである。The dielectric porcelain substrate provided by the present invention (hereinafter referred to as the dielectric porcelain substrate of the present invention) has an insulating layer at the grain boundaries of the semiconductor porcelain made of the fired body of the ceramic forming composition of the present invention. It is characterized by this.
本発明によって提供されるコンデンサー（以下、本発明
のコンデンサーといら）は、一対の電極と；該電極に挟
持された本発明のセラミック形成組成物の焼成体から成
る半導体磁器の結晶粒界に絶縁層が存在している誘電体
磁器と；を有していることを特徴とするものである。The capacitor provided by the present invention (hereinafter referred to as the capacitor of the present invention) is insulated at the grain boundaries of a semiconductor porcelain comprising a pair of electrodes; and a fired body of the ceramic forming composition of the present invention sandwiched between the electrodes. It is characterized by having a layer of dielectric ceramic;
本発明のセラミック形成組成物には、前記ＴｉＱ ２
、 ＳｒＯ、ＭｎＯ２及びＷＯ３以外の成分として５
ｉ０２が含有され得る。 ＳｉＯ□の好適な含量は、前
記ＴｉＯ□５０．２０〜５３．５０モル％及びＳｒＯ４
９，８０〜４８．５０モル％から成る主成分１００モル
部に対して０．０１〜２．００モル部である。The ceramic forming composition of the present invention includes the TiQ 2
, 5 as components other than SrO, MnO2 and WO3
i02 may be included. A suitable content of SiO□ is 50.20 to 53.50 mol% of the TiO□ and SrO4
The amount is 0.01 to 2.00 mol parts per 100 mol parts of the main component consisting of 9.80 to 48.50 mol%.
以下、本発明の構成について更に詳しく説明する。Hereinafter, the configuration of the present invention will be explained in more detail.
本発明のセラミック形成用組成物において、主成分であ
るＴｉ０２とＳｒＯは、固溶体等の複合酸化物、ＴｉＯ
□、 ＳｒＯ夫々の単独酸化物、あるいはこれらの混合
物として組成物中に存在し得る。組成物中におけるＴｉ
Ｏ２とＳｒＯの量比を、Ｔｉ０７ ５０゜２０ 〜５３
．５０モル％に対しＳｒＯ４９．８０〜４６．５’３モ
ル％としたのは、Ｔｉ０２の量が多くなると、即ちＳｒ
Ｏの量が少なくなると、所望する誘電体磁器の誘電率が
低下し、誘電損失と誘電率の温度変化が大きくなり、し
かも磁器の絶縁抵抗が減少する。 Ｔｉ０２の量が少な
くなると、即ちＳｒＯの量が多くなると、所望する誘電
体磁器の誘電率が低下し、誘電率の温度変化が大きくな
る。本発明組成物中におけるＴｉＯ２とＳｒＯの量比は
、これらの誘電率、誘電損失、誘電率の温度変化、磁器
の絶縁抵抗、半導体化能といった所望特性をバランス良
く最適に発現させるために決定される。In the composition for forming ceramics of the present invention, the main components Ti02 and SrO are mixed with a composite oxide such as a solid solution, TiO2
□, SrO may be present in the composition as a single oxide, or as a mixture thereof. Ti in the composition
The amount ratio of O2 and SrO is Ti07 50°20 ~ 53
．． The reason for setting SrO49.80 to 46.5'3 mol% to 50 mol% is that as the amount of Ti02 increases, that is, SrO
When the amount of O decreases, the dielectric constant of the desired dielectric ceramic decreases, the dielectric loss and the temperature change in the dielectric constant increase, and the insulation resistance of the ceramic decreases. When the amount of Ti02 decreases, that is, when the amount of SrO increases, the dielectric constant of the desired dielectric ceramic decreases, and the temperature change in the dielectric constant increases. The quantitative ratio of TiO2 and SrO in the composition of the present invention is determined in order to optimally express desired properties such as dielectric constant, dielectric loss, temperature change in dielectric constant, insulation resistance of ceramics, and semiconductor ability in a well-balanced manner. Ru.
本発明のセラミック形成組成物においてＭｎＯ２は磁器
を形成するための焼結助剤の役割を有するものであり、
その使用量を前記↑１０□及びＳｒＯから成る主成分１
００モル部に対して３．０モル部以上に限定したのは、
ＭｎＯ２が３．０モル部未満であると所望する誘電体磁
器の誘電率が低下すると共に誘電率の温度変化が大きく
なるからである。前記Ｔｉ０２及びＳｒＯから成る主成
分１００モル部に対して５．０モル部以下に限定したの
は、ＭｎＯ２が５．０モル部を越えると誘電損失の増加
が顕著となるためである。なお、このＭｎＯ７に関し、
本発明は、特開昭５４−７８４９８号に記載された磁器
組成物に比べて使用量が多いので粒界面の改良効果が大
きいなど、非常に良好である。In the ceramic forming composition of the present invention, MnO2 has the role of a sintering aid for forming porcelain,
The amount used is the main component 1 consisting of the above ↑10□ and SrO.
00 mole parts is limited to 3.0 mole parts or more because
This is because if MnO2 is less than 3.0 mol parts, the dielectric constant of the desired dielectric ceramic will decrease and the temperature change in the dielectric constant will increase. The reason why the amount of MnO2 is limited to 5.0 mol parts or less per 100 mol parts of the main component consisting of Ti02 and SrO is that if MnO2 exceeds 5.0 mol parts, the increase in dielectric loss becomes significant. Regarding this MnO7,
The present invention is very good in that it uses a larger amount than the porcelain composition described in JP-A-54-78498, so the effect of improving grain boundaries is greater.
次に１本発明のセラミック形成組成物において、ＷＯ３
は磁器の半導体化に効果を有するものであり、その使用
量を前記ＴｉＯ２及びＳｒＯから成る主成分１００モル
部に対して０．０５モル部以上に限定したのは、Ｘ１１
０３が０．０５モル部未満であると磁器の半導体化が不
十分となり、誘電率が低下するためである。前記Ｔｉｎ
２及びＳｒＯから成る主成分１００モル部に対して０
．３モル部以下に限定したのは、誓０３が０．３モル部
を越えると誘電率が低下し、誘電損失が大きくなるため
である。Next, in one ceramic forming composition of the present invention, WO3
is effective in converting ceramics into semiconductors, and the reason why its usage was limited to 0.05 mol parts or more per 100 mol parts of the main components consisting of TiO2 and SrO was because X11
This is because if the amount of 03 is less than 0.05 mole part, the semiconducting of the ceramic will be insufficient and the dielectric constant will decrease. Said Tin
0 per 100 mol parts of the main component consisting of 2 and SrO
．． The reason why the content is limited to 3 parts by mole or less is because if O3 exceeds 0.3 parts by mole, the dielectric constant decreases and dielectric loss increases.
また、本発明のセラミック形成組成物に所望により加え
られる成分であるＳｉＯ□は半導体磁器の粒界面改良剤
としての作用を有するものである。Further, SiO□, which is a component optionally added to the ceramic forming composition of the present invention, functions as a grain interface improving agent for semiconductor ceramics.
この粒界面改良剤とは、半導体磁器の表面に結晶粒界へ
の拡散成分となる添加剤を添布した後、空気等の酸化雰
囲気中で焼成し、結晶粒界に添加剤を拡散させる際に、
該添加剤の粒界面への拡散を均一にすることにより、所
望する誘電体磁器の誘電率の向ヒ、並びに特性の安定化
、誘電損失の低下に寄与する。但し、この様な効果を期
待して、ＳｉＯ２を使用する場合に、ＳｉＯ２の使用量
が前記Ｔｉ０２及びＳｒＯから成る主成分１００モル部
に対し０．０１モル部未満であると効果が十分に発現さ
れず、２．００モル部を越えると結晶粒界の絶縁層の厚
みが増し所望する誘電体磁器の誘電率が低下し、好まし
くない、 ＳｉＯ２の使用量のより好ましくは、前記Ｔ
ｉＯ２及びＳｒＯから成る主成分１００モル部に対し０
．２０〜２．００モル部である。This grain interface improver is a process in which an additive that becomes a diffusion component to the grain boundaries is added to the surface of semiconductor porcelain, and then fired in an oxidizing atmosphere such as air to diffuse the additive into the grain boundaries. To,
Uniform diffusion of the additive to the grain interface contributes to increasing the dielectric constant of the desired dielectric ceramic, stabilizing the characteristics, and reducing dielectric loss. However, when using SiO2 in anticipation of such an effect, the effect can be fully expressed if the amount of SiO2 used is less than 0.01 mole part per 100 mole parts of the main component consisting of Ti02 and SrO. If the amount exceeds 2.00 mol parts, the thickness of the insulating layer at the grain boundary increases and the dielectric constant of the desired dielectric ceramic decreases, which is undesirable.
0 per 100 mol parts of the main component consisting of iO2 and SrO
．． It is 20 to 2.00 mole parts.
この様に構成される本発明のセラミツ形成組成物を用い
て本発明の半導体磁器基体を得るには、本発明のセラミ
ック形成組成物の成形体（圧粉体）を調製し、これを焼
成する方法が一般的である０例えば、ＴｉＯ２、ＳｒＯ
、ＭｎＯ７ 、 ＷＯ３及び所望に応じて加えられるＳ
ｉＯ２の各成分を含む原料粉末にポリビニルアルコール
などのバインダーを加え造粒を行ないプレス成形にて成
形体（圧粉体）を得る０次いで、この成形体からバイン
ダーを除くため酸化雰囲気中６００−１２００℃〒仮焼
する。この仮焼体を、次いで水素と窒素の混合ガス、水
素とアルゴンの混合ガス等の還元雰囲気あるいは窒素、
アルゴン等の中性雰囲気中、より好ましくは還元雰囲気
中、望ましくは１３２０℃〜１４５０℃で焼成して半導
体磁器基体を得る。In order to obtain the semiconductor ceramic substrate of the present invention using the ceramic-forming composition of the present invention configured as described above, a molded body (green compact) of the ceramic-forming composition of the present invention is prepared and then fired. The method is common 0 e.g. TiO2, SrO
, MnO7, WO3 and optionally S
A binder such as polyvinyl alcohol is added to the raw material powder containing each component of iO2, granulation is performed, and a compact is obtained by press molding.Next, in order to remove the binder from this compact, it is heated at 600 to 1200 in an oxidizing atmosphere. ℃〒Calcinate. This calcined body is then heated in a reducing atmosphere such as a mixed gas of hydrogen and nitrogen, a mixed gas of hydrogen and argon, or nitrogen.
A semiconductor ceramic substrate is obtained by firing in a neutral atmosphere such as argon, more preferably in a reducing atmosphere, preferably at 1320°C to 1450°C.
また、例えば前述した方法により得られる本発明のセラ
ミック形成組成物を用いた半導体磁器の結晶粒界に絶縁
層を形成することにより１本発明の絶縁体磁器基体を得
ることができる。絶縁層の形成方法としては、結晶粒界
への拡散成分となる添加剤を半導体磁器基体の表面に塗
布して焼成する方法が挙げられる。焼成は酸化雰囲気中
で１１００〜１３００℃で行なうのが望ましい。Furthermore, the insulating ceramic substrate of the present invention can be obtained by forming an insulating layer at the grain boundaries of semiconductor ceramic using the ceramic forming composition of the present invention obtained by the method described above, for example. An example of a method for forming the insulating layer is a method in which an additive that becomes a component diffusing into grain boundaries is applied to the surface of a semiconductor ceramic substrate and then fired. The firing is preferably carried out at 1100 to 1300°C in an oxidizing atmosphere.
添加剤としては、半導体磁器の結晶粒界に絶縁層を形成
するための従来公知の添加剤の何れをも使用することが
できる０例えば、鉄、コバルト、ビスマス、バナジウム
、クロム、鉛等の酸化物のほか、特に本発明において好
適に用いられるのは、酸化ホウ素及び酸化ナトリ゛ウム
であり、これらを用いた場合本発明の目的とする誘電体
磁器の誘電率、温度特性、並びに誘電損失の改良効果に
関して良好な結果が得られる。添加剤は、焼成の結果と
してこれら酸化物の形態をとればよく、半導体磁器表面
に供給するときは、例えば酸化物、窒化物、炭酸塩等の
形態でよい。As the additive, any of the conventionally known additives for forming an insulating layer at the grain boundaries of semiconductor porcelain can be used. For example, oxidation of iron, cobalt, bismuth, vanadium, chromium, lead, etc. Boron oxide and sodium oxide are particularly preferably used in the present invention, and when these are used, the dielectric constant, temperature characteristics, and dielectric loss of the dielectric ceramic, which are the objects of the present invention, can be improved. Good results are obtained regarding the improvement effect. The additive may be in the form of these oxides as a result of firing, and when supplied to the surface of the semiconductor ceramic, it may be in the form of, for example, oxides, nitrides, carbonates, etc.
更に、例えば前述した方法により得られる本発明のセラ
ミック形成組成物を用いた誘電体磁器を一対の電極に挟
持することにより、本発明のコンデンサーを構成するこ
とができる。Furthermore, the capacitor of the present invention can be constructed by sandwiching a dielectric ceramic using the ceramic forming composition of the present invention obtained by the method described above between a pair of electrodes.
第１図及び第２図には、本発明のコンデンサーの一例が
示されている。第１図はコンデンサーの模式的斜視図、
第２図は模式的切断面部分図である。1 and 2 show an example of the capacitor of the present invention. Figure 1 is a schematic perspective view of a capacitor.
FIG. 2 is a schematic partial cross-sectional view.
図に示したコンデンサーは、例えば円板状の誘電体磁器
層１２の上下の面に、夫々Ａ見、Ａｕ。The capacitor shown in the figure has, for example, a disc-shaped dielectric ceramic layer 12 with A and Au layers on the upper and lower surfaces, respectively.
Ａｇ、Ｎｉ等で構成される電極１１（図には、上面の電
極しか示されてない）が設けられて構成されている。誘
電体磁器層１２は、半導体磁器の結晶粒２２の多数を粒
界に形成された絶縁層２１を介在した形で含有している
。An electrode 11 (only the top electrode is shown in the figure) made of Ag, Ni, etc. is provided. The dielectric ceramic layer 12 contains a large number of semiconductor ceramic crystal grains 22 with an insulating layer 21 formed at the grain boundaries interposed therebetween.
結晶粒２２の大きさは、要求される電気的特性と構成材
料の配合量、焼成条件等によって適宜決定されるが、通
常の場合、１糾ｍ”１００ｇｍ、好ましくは２ｇ、ｍ〜
８０ ｇｍとされるのが望ましい。The size of the crystal grains 22 is appropriately determined depending on the required electrical properties, the amount of constituent materials, the firing conditions, etc., but in normal cases it is 100 gm, preferably 2 g, m~
Preferably, it is 80 gm.
［実施例］
以下に具体的実施例を示して、本発明を更に詳しく説明
する。[Example] The present invention will be explained in more detail by showing specific examples below.
実施例１
第１表に示す組成比率の半導体磁器が得られるように、
Ｔｉ０２ 、 ＷＯ３、５ｉＯ１、ＳｒＯ９ＭｎＯ２
の各原料を秤取し、湿式ボールミルで１２時間粉砕混合
を行なった。このものを乾燥後少量のポリビニルアルコ
ールをバインダーとして加え２４〜８０メツシユに造粒
し油圧プレスによって直径２０ｍｍ、厚さ０．８■の円
板に成型した０次いで、この成形円板を大気中９５０℃
で１時間仮焼してバインダーを燃焼させた。これを室温
まで冷却後、水素１０容量％、窒素９０容量％からなる
還元雰囲気中で１４００℃で４時間焼成した。Example 1 In order to obtain semiconductor porcelain having the composition ratio shown in Table 1,
Ti02, WO3, 5iO1, SrO9MnO2
Each of the raw materials was weighed out and pulverized and mixed in a wet ball mill for 12 hours. After drying, a small amount of polyvinyl alcohol was added as a binder, and the mixture was granulated into 24 to 80 meshes, and then molded into a disc with a diameter of 20 mm and a thickness of 0.8 cm using a hydraulic press. ℃
The binder was burned by calcination for 1 hour. After cooling this to room temperature, it was fired at 1400° C. for 4 hours in a reducing atmosphere consisting of 10% by volume hydrogen and 90% by volume nitrogen.
こうして得られた半導体磁器に、重量比がエチルアルコ
ール：Ｂ２Ｏ３又はＮａ２０ ＝ ｌ Ｏ： １となる
懸濁液にドブ浸は後、１２５０℃、０．５時間、酸化雰
囲気にて焼成して結晶粒界に絶縁層を形成した。The semiconductor porcelain thus obtained was immersed in a suspension of ethyl alcohol: B2O3 or Na20 = 1 O: 1 by weight, and then fired at 1250°C for 0.5 hours in an oxidizing atmosphere to form crystal grains. An insulating layer was formed in the field.
かくして得られた誘電体磁器の円板（試料ＮＯ。The thus obtained dielectric porcelain disk (sample no.
１〜２５）の両面に銀ペーストを塗布し、８５０℃、３
０分焼付して電極を形成しコンデンサを作製した。Apply silver paste to both sides of 1 to 25) and heat at 850℃ for 3
After baking for 0 minutes, electrodes were formed and a capacitor was manufactured.
こうして得られたコンデンサーを構成する誘電体磁器の
誘電率（ε）、誘電損失（ｔａｎ δ）、絶縁抵抗（Ｉ
Ｒ）および誘電率の温度特性（２５℃を基準とする一２
５℃、＋８５℃における温度変化率）を測定し、その結
果を第２表に示した。測定条件は２５℃、周波数１ ｋ
Ｈｚである。なお表１．２中の木は本発明の範囲外にあ
る試料である。 第１表、第２表に示される通り本発明
のコンデンサー用のセラミック形成組成物を用いた誘電
体磁器は、従来のものと比較して、誘電率が７５０００
〜１１９０００以上と高（ｔａｎδが１％以内であり絶
縁抵抗４０００ＭΩ以上あり２５℃基準の一２５℃〜８
５℃の誘電率の温度変化率が±１０％以内であり極めて
良好な特性を示した。The dielectric constant (ε), dielectric loss (tan δ), and insulation resistance (I
R) and temperature characteristics of dielectric constant (25°C as standard)
The temperature change rate at 5° C. and +85° C.) was measured, and the results are shown in Table 2. Measurement conditions are 25℃, frequency 1k
It is Hz. Note that the trees in Table 1.2 are samples outside the scope of the present invention. As shown in Tables 1 and 2, the dielectric ceramic using the ceramic forming composition for capacitors of the present invention has a dielectric constant of 75,000 compared to the conventional one.
- High at 119,000 or more (tan δ is within 1%, insulation resistance is 4,000 MΩ or more, 25°C standard - 25°C - 8
The temperature change rate of dielectric constant at 5° C. was within ±10%, showing extremely good characteristics.
第 １ 表
（＊は本発明範囲外、以下の頁の表において同じ）第
１ 表（つづき）
第 ２ 表
第 ２ 表（つづき）
［発明の効果］
前記実施例から明らかな様に、本発明のセラミック形成
組成物によれば、誘電率（ε）が７５，０００以上と高
く、誘電損失（ｔａｎδ）１％以下、′絶縁抵抗４００
０ＭΩ以上といった高特性にもかかわらず、誘電率の温
度変化が一２５℃〜＋８５℃において±１０％以内と良
好な高特性の誘電体磁器を構成することができる。Table 1 (* indicates outside the scope of the present invention; the same applies to the tables on the following pages)
1 Table (Continued) Table 2 Table 2 (Continued) [Effects of the Invention] As is clear from the above examples, the ceramic forming composition of the present invention has a dielectric constant (ε) of 75,000 or more. High dielectric loss (tan δ) 1% or less, insulation resistance 400
In spite of the high characteristics of 0 MΩ or more, it is possible to construct a dielectric ceramic with excellent characteristics such that the temperature change in the dielectric constant is within ±10% from 125° C. to +85° C.
この様に、本発明のセラミック形成組成物、半導体磁器
基体、誘電体磁器基体は、高性能のコンデンサーを構成
し得る。In this way, the ceramic forming composition, semiconductor ceramic substrate, and dielectric ceramic substrate of the present invention can constitute a high performance capacitor.
第１図は本発明のコンデンサーの一例を示した模式的斜
視図、第２図はその模式的切断面部分図である。
１２・・・誘電体磁器
１１・・・電極。
代理人 弁理士 山 下 穣 平
第１図
第２図FIG. 1 is a schematic perspective view showing an example of the capacitor of the present invention, and FIG. 2 is a schematic cross-sectional partial view thereof. 12... Dielectric ceramic 11... Electrode. Agent Patent Attorney Johei Yamashita Figure 1 Figure 2
Claims (8)
ｒＯ４９．８０〜４６．５０モル％から成る主成分１０
０モル部に対し、ＭｎＯ＿２３．０〜５．０モル部、並
びにＷＯ＿３０．０５〜０．３０モル部が含有されてい
ることを特徴とするセラミック形成組成物。(1) TiO_250.20-53.50 mol% and S
Main component 10 consisting of rO49.80-46.50 mol%
A ceramic-forming composition characterized in that 23.0 to 5.0 mole parts of MnO and 30.05 to 0.30 mole parts of WO are contained relative to 0 mole part.
し、更にＳｉＯ＿２０．０１〜２．００モル部が含有さ
れている特許請求の範囲第（１）項記載のセラミック形
成組成物。(2) The ceramic-forming composition according to claim (1), further containing 20.01 to 2.00 mole parts of SiO with respect to 100 mole parts of the main component of the ceramic-forming composition.
ｒＯ４９．８０〜４８．５０モル％から成る主成分１０
０モル部に対し、ＭｎＯ＿２３．０〜５．０モル部、並
びにＷＯ＿３０．０５〜０．３０部が含有されているセ
ラミック形成組成物の焼成体から成ることを特徴とする
半導体磁器基体。(3) TiO_250.20-53.50 mol% and S
Main component 10 consisting of rO49.80-48.50 mol%
A semiconductor ceramic substrate comprising a fired body of a ceramic forming composition containing 23.0 to 5.0 mole parts of MnO and 30.05 to 0.30 parts of WO based on 0 mole part.
し、更にＳｉＯ＿２０．０１〜２．００モル部が含有さ
れている特許請求の範囲第（３）項記載の半導体磁器基
体。(4) The semiconductor ceramic substrate according to claim (3), further containing 20.01 to 2.00 mole parts of SiO with respect to 100 mole parts of the main component of the ceramic forming composition.
ｒＯ４９．８０〜４６．５０モル％から成る主成分１０
０モル部に対し、ＭｎＯ＿２３．０〜５．０モル部、並
びにＷＯ＿３０．０５〜０．３０モル部が含有されてい
るセラミック形成組成物の焼成体から成る半導体磁器の
結晶粒界に絶縁層が存在していることを特徴とする誘電
体磁器基体。(5) TiO_250.20-53.50 mol% and S
Main component 10 consisting of rO49.80-46.50 mol%
An insulating layer is formed at the grain boundaries of a semiconductor ceramic made of a fired body of a ceramic forming composition containing 0 mole part of MnO_23.0 to 5.0 mole part and WO_30.05 to 0.30 mole part. A dielectric ceramic substrate characterized by the presence of a dielectric ceramic substrate.
し、更にＳｉＯ＿２０．０１〜２．００モル部が含有さ
れている特許請求の範囲第（５）項記載の誘電導体磁器
体。(6) The dielectric conductor ceramic body according to claim (5), further containing 20.01 to 2.00 mole parts of SiO with respect to 100 mole parts of the main component of the ceramic forming composition.
３．８０〜４６．５０モル％から成る主成分１００モル
部に対し、ＭｎＯ＿２３．０〜５．０モル部、並びにＷ
Ｏ＿３０．０５〜０．３０モル部が含有されているセラ
ミック形成組成物の焼成体から成る半導体磁器の結晶粒
界に絶縁層が存在している誘電体磁器と；を有している
ことを特徴とするコンデンサー。(7) a pair of electrodes; sandwiched between the electrodes, TiO_250.20 to 53.50 mol% and SrO4
MnO_23.0 to 5.0 mol parts and W
A dielectric porcelain in which an insulating layer is present at the grain boundaries of a semiconductor porcelain made of a fired body of a ceramic-forming composition containing 0.05 to 0.30 mol parts of O_30. capacitor.
し、更にＳｉＯ＿２０、０１〜２．００モル部が含有さ
れている特許請求の範囲第（７）項記載のコンデンサー
。(8) The capacitor according to claim (7), further comprising 01 to 2.00 mole parts of SiO_20, based on 100 mole parts of the main component of the ceramic forming composition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61158466A JP2576973B2 (en) | 1986-07-05 | 1986-07-05 | Ceramic forming composition and semiconductor and dielectric ceramic substrates and capacitors using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61158466A JP2576973B2 (en) | 1986-07-05 | 1986-07-05 | Ceramic forming composition and semiconductor and dielectric ceramic substrates and capacitors using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6316504A true JPS6316504A (en) | 1988-01-23 |
| JP2576973B2 JP2576973B2 (en) | 1997-01-29 |
Family
ID=15672355
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61158466A Expired - Fee Related JP2576973B2 (en) | 1986-07-05 | 1986-07-05 | Ceramic forming composition and semiconductor and dielectric ceramic substrates and capacitors using the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2576973B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01266260A (en) * | 1988-04-18 | 1989-10-24 | Toray Ind Inc | Water-absorptive cloth and production thereof |
| JPH04241160A (en) * | 1990-07-02 | 1992-08-28 | Polyfelt Gmbh | Method for producing needle span bond cloth |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5727001A (en) * | 1980-07-25 | 1982-02-13 | Tdk Electronics Co Ltd | Voltage nonlinear resistance element |
| JPS632310A (en) * | 1986-06-23 | 1988-01-07 | 和久 茂 | Grain boundary insulating type semiconductor porcelain compound |
-
1986
- 1986-07-05 JP JP61158466A patent/JP2576973B2/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5727001A (en) * | 1980-07-25 | 1982-02-13 | Tdk Electronics Co Ltd | Voltage nonlinear resistance element |
| JPS632310A (en) * | 1986-06-23 | 1988-01-07 | 和久 茂 | Grain boundary insulating type semiconductor porcelain compound |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01266260A (en) * | 1988-04-18 | 1989-10-24 | Toray Ind Inc | Water-absorptive cloth and production thereof |
| JPH04241160A (en) * | 1990-07-02 | 1992-08-28 | Polyfelt Gmbh | Method for producing needle span bond cloth |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2576973B2 (en) | 1997-01-29 |
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