JPH04349302A - Compound for reduction oxidization type semiconductor ceramic condenser - Google Patents
Compound for reduction oxidization type semiconductor ceramic condenserInfo
- Publication number
- JPH04349302A JPH04349302A JP3149206A JP14920691A JPH04349302A JP H04349302 A JPH04349302 A JP H04349302A JP 3149206 A JP3149206 A JP 3149206A JP 14920691 A JP14920691 A JP 14920691A JP H04349302 A JPH04349302 A JP H04349302A
- Authority
- JP
- Japan
- Prior art keywords
- reduction
- type semiconductor
- capacitance
- composition
- breakdown voltage
- 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
- 239000004065 semiconductor Substances 0.000 title claims abstract description 29
- 239000000919 ceramic Substances 0.000 title abstract description 16
- 150000001875 compounds Chemical class 0.000 title abstract description 5
- 238000007254 oxidation reaction Methods 0.000 title 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 13
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910002113 barium titanate Inorganic materials 0.000 claims abstract description 10
- 229910021523 barium zirconate Inorganic materials 0.000 claims abstract description 8
- 229910002370 SrTiO3 Inorganic materials 0.000 claims abstract description 6
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 6
- 229910052802 copper Inorganic materials 0.000 claims abstract description 6
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 6
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 5
- 229910052692 Dysprosium Inorganic materials 0.000 claims abstract description 5
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 5
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 5
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 5
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 5
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 5
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 5
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 5
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 5
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims description 37
- 238000010405 reoxidation reaction Methods 0.000 claims description 18
- 239000003985 ceramic capacitor Substances 0.000 claims description 17
- 229910016264 Bi2 O3 Inorganic materials 0.000 claims description 4
- 230000015556 catabolic process Effects 0.000 abstract description 24
- 238000009413 insulation Methods 0.000 abstract description 24
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052742 iron Inorganic materials 0.000 abstract description 4
- 229910052715 tantalum Inorganic materials 0.000 abstract description 3
- 239000003990 capacitor Substances 0.000 description 13
- 230000000694 effects Effects 0.000 description 9
- 229910052573 porcelain Inorganic materials 0.000 description 7
- 239000006104 solid solution Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 2
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 150000002603 lanthanum Chemical class 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 2
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N CuO Inorganic materials [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 229910017344 Fe2 O3 Inorganic materials 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229910002367 SrTiO Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- GHPGOEFPKIHBNM-UHFFFAOYSA-N antimony(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Sb+3].[Sb+3] GHPGOEFPKIHBNM-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(II) oxide Inorganic materials [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- NLQFUUYNQFMIJW-UHFFFAOYSA-N dysprosium(III) oxide Inorganic materials O=[Dy]O[Dy]=O NLQFUUYNQFMIJW-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229940093474 manganese carbonate Drugs 0.000 description 1
- 235000006748 manganese carbonate Nutrition 0.000 description 1
- 239000011656 manganese carbonate Substances 0.000 description 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 1
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium oxide Inorganic materials [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- LEDMRZGFZIAGGB-UHFFFAOYSA-L strontium carbonate Chemical compound [Sr+2].[O-]C([O-])=O LEDMRZGFZIAGGB-UHFFFAOYSA-L 0.000 description 1
- 229910000018 strontium carbonate Inorganic materials 0.000 description 1
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten(VI) oxide Inorganic materials O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は再酸化半導体セラミック
コンデンサのためのセラミック組成物に関する。FIELD OF THE INVENTION This invention relates to ceramic compositions for reoxidized semiconductor ceramic capacitors.
【０００２】0002
【従来の技術】近年の電子機器の小型化、高密度実装化
並びに品質の高安定化に伴い、電子部品にも小型化と高
品質化の要求がなされており、高い絶縁抵抗、破壊電圧
を有しあわせて小型大容量で且つ誘電損失の小さい還元
再酸化型半導体セラミックコンデンサの開発が要望され
ている。従来、還元再酸化型半導体セラミックコンデン
サ用組成物に関しては、例えばＢａＴｉＯ３ −Ｌａ２
Ｏ３ −ＴｉＯ２ 系固溶体組成物及びこの固溶体に
炭酸マンガンを０．６重量％以下添加した組成が知られ
ており、この組成物よりなるセラミックコンデンサでは
単位面積当たりの容量が０．２７μＦ／ｃｍ２ 、誘電
損失ｔａｎδが２．８％、破壊電圧が８００Ｖの特性が
得られている（特公昭５１−４４７３８号公報）。[Background Art] With the recent miniaturization, high-density packaging, and highly stable quality of electronic devices, there is a demand for miniaturization and high quality of electronic components, and high insulation resistance and breakdown voltage are required. There is a demand for the development of a reduction-reoxidation type semiconductor ceramic capacitor that is small in size, has a large capacity, and has low dielectric loss. Conventionally, regarding reduction and reoxidation type semiconductor ceramic capacitor compositions, for example, BaTiO3-La2
O3 -TiO2 solid solution compositions and compositions in which 0.6% by weight or less of manganese carbonate is added to this solid solution are known, and a ceramic capacitor made of this composition has a capacitance per unit area of 0.27 μF/cm2 and a dielectric Characteristics of loss tan δ of 2.8% and breakdown voltage of 800 V have been obtained (Japanese Patent Publication No. 44738/1983).
【０００３】又、ＢａＴｉＯ３ −ＳｒＴｉＯ３ −Ｌ
ｎ２ Ｏ３ （Ｌｎ；ランタン系列元素）−ＴｉＯ２
系固溶体組成物にＣｒ、Ｍｎ、Ｆｅ、Ｃｏ及びＮｉの酸
化物を１原子％以下及びＳｉの酸化物を２原子％以下添
加した組成が知られており、この組成物よりなるセラミ
ックコンデンサでは単位面積当たりの容量が０．５８μ
Ｆ／ｃｍ２ 、ｔａｎδ２．８％、破壊電圧が８２０Ｖ
の特性が得られている（特開昭５８−１４５１８号公報
）。[0003] Also, BaTiO3 -SrTiO3 -L
n2 O3 (Ln; lanthanum series element)-TiO2
A composition in which oxides of Cr, Mn, Fe, Co, and Ni are added at 1 atomic % or less and an oxide of Si at 2 atomic % or less is added to a solid solution composition is known. Capacity per area is 0.58μ
F/cm2, tan δ2.8%, breakdown voltage 820V
The following characteristics have been obtained (Japanese Unexamined Patent Publication No. 14518/1983).
【０００４】一般的には表面部の薄い誘電体層が、還元
再酸化型半導体セラミックコンデンサの容量、絶縁抵抗
、破壊電圧及び誘電損失に大きく関与している。誘電体
層を薄くすると、コンデンサの単位面積当たりの容量は
大きくなるが、必然的に絶縁抵抗及び破壊電圧は低下し
、逆に絶縁抵抗及び破壊電圧を高くしようとすると誘電
体層も厚くする必要があり、単位面積当たりの容量が低
下するという性質を有している。又、コンデンサの誘電
損失は、誘電体層のｔａｎδに依存するが、それ以上に
誘電体層と半導体セラミックの境界の直列抵抗分が大き
く関与する。ｔａｎδを小さくするためには、この直列
抵抗分を小さくする必要がある。特にｔａｎδはコンデ
ンサの重要な特性であるので、その値の増加は大きな欠
点となり、且つ少しでもその値を低下させることが種々
の改良の大きな課題であった。このためにはコンデンサ
とした場合に誘電体層の単位層厚当たりの抵抗値及び破
壊電圧が高く且つ直列抵抗分の低いセラミック組成物の
新たな選択が必要である。[0004] Generally, the thin dielectric layer on the surface has a large influence on the capacitance, insulation resistance, breakdown voltage, and dielectric loss of the reduction-reoxidation type semiconductor ceramic capacitor. When the dielectric layer is made thinner, the capacitance per unit area of the capacitor increases, but the insulation resistance and breakdown voltage inevitably decrease. Conversely, if you try to increase the insulation resistance and breakdown voltage, you need to make the dielectric layer thicker. It has the property that the capacity per unit area decreases. Further, although the dielectric loss of a capacitor depends on the tan δ of the dielectric layer, the series resistance at the boundary between the dielectric layer and the semiconductor ceramic is more significantly involved. In order to reduce tan δ, it is necessary to reduce this series resistance. In particular, since tan δ is an important characteristic of capacitors, an increase in its value would be a major drawback, and reducing its value as much as possible has been a major challenge for various improvements. For this purpose, it is necessary to newly select a ceramic composition that has a high resistance value and breakdown voltage per unit layer thickness of the dielectric layer and a low series resistance when used as a capacitor.
【０００５】本発明者らは、特願昭６３−１３５６９５
号において、ＢａＴｉＯ３ −ＳｒＴｉＯ３ −Ｌｎ２
Ｏ３ （Ｌｎ；ランタン系列元素）−ＴｉＯ２ 系固
溶体組成物にＣｕ、Ｚｎ、Ａｌ、Ｍｇ及びＭｏの各酸化
物の少なくとも一種を０．００１〜１重量％含有してい
る還元再酸化型半導体コンデンサ用セラミック組成物に
おいて、破壊電圧９００Ｖ以上、絶縁抵抗１０１０Ω以
上で、単位面積当たりの容量が０．６０μＦ／ｃｍ２
を越え、しかも、ｔａｎδが２．０％未満という特性を
得た。[0005] The present inventors have applied for patent application No. 63-135695.
In the issue, BaTiO3 -SrTiO3 -Ln2
O3 (Ln; lanthanum series element) - TiO2 based solid solution composition containing 0.001 to 1% by weight of at least one of Cu, Zn, Al, Mg and Mo oxides for a reduction and reoxidation type semiconductor capacitor The ceramic composition has a breakdown voltage of 900 V or more, an insulation resistance of 1010 Ω or more, and a capacitance per unit area of 0.60 μF/cm2.
In addition, the properties of tan δ of less than 2.0% were obtained.
【０００６】一方、静電容量の温度特性を±２０〜±３
０％以内にした場合の還元再酸化型半導体セラミックコ
ンデンサ用組成物に関しては、特開昭５３−１１４１０
０号公報においてＢａＴｉＯ３ −ＢａＺｒＯ３ −Ｂ
ｉ２ Ｏ３ −ＴｉＯ２ 系固溶体にＮｉ化合物を添加
した磁器材料が開示されており、この材料からなる磁器
コンデンサでは単位面積当たり０．５７μＦ／ｃｍ２
、ｔａｎδ±４．３％、絶縁抵抗２００ＭΩ／ｃｍ２
（１５ＶＤＣ．１５秒後）、容量の−３０〜８５℃の温
度特性（％）が±３０％以内、の特性が得られている。
又、特開昭６２−３０４８１号公報においてはＢａＴｉ
Ｏ３ −ＢａＺｒＯ３ −Ｂｉ２ Ｏ３ −ＺｒＯ２
系固溶体にＮｉ化合物を添加した磁器材料が開示されて
おり、この材料からなる磁器コンデンサでは単位面積当
たり０．６０μＦ／ｃｍ２ 、ｔａｎδ４．５％、絶縁
抵抗２１０ＭΩ／ｃｍ２ （１５ＶＤＣ．１５秒後）、
容量の−３０〜８５℃の温度特性（％）が±３０％以内
、の特性が得られている。On the other hand, the temperature characteristic of capacitance is ±20 to ±3
Regarding compositions for reduction and reoxidation type semiconductor ceramic capacitors when the content is within 0%, Japanese Patent Application Laid-Open No. 53-11410
In Publication No. 0, BaTiO3 -BaZrO3 -B
A ceramic material in which a Ni compound is added to an i2 O3 -TiO2 solid solution is disclosed, and a ceramic capacitor made of this material has a capacitance of 0.57 μF/cm2 per unit area.
, tan δ±4.3%, insulation resistance 200MΩ/cm2
(15 VDC, after 15 seconds), the temperature characteristic (%) of the capacity from -30 to 85°C was within ±30%. Moreover, in Japanese Patent Application Laid-Open No. 62-30481, BaTi
O3 -BaZrO3 -Bi2 O3 -ZrO2
A ceramic material in which a Ni compound is added to a solid solution is disclosed, and a ceramic capacitor made of this material has a resistance per unit area of 0.60 μF/cm2, a tan δ of 4.5%, an insulation resistance of 210 MΩ/cm2 (15 VDC, after 15 seconds),
The temperature characteristic (%) of the capacity from -30 to 85° C. is within ±30%.
【０００７】しかしながら、還元再酸化型半導体セラミ
ックコンデンサにおいては、各種の性能向上の要望は強
く、静電容量の温度特性が良く、破壊電圧が４００Ｖ以
上、単位面積当たりの容量が大きく、誘電損失も更に低
いという特性を有する組成物の開発が切望されていた。
本発明者らは、特願昭６３−１６２５６８号において、
ＢａＴｉＯ３ −ＢａＺｒＯ３ −Ｂｉ２Ｏ３ −Ｔｉ
Ｏ２ 又はＺｒＯ２ 系固溶体にＣｒ、Ｆｅ、Ｃｏ、Ｚ
ｎ、Ｃｕ、Ａｌ、Ｓｉ及び、Ｍｇの各酸化物の少なくと
も一種が０．００１〜１．００重量％含有している還元
再酸化型半導体コンデンサ用セラミック組成物において
、破壊電圧４００Ｖ以上、絶縁抵抗１０９ Ω以上で、
単位面積当たりの容量が０．６５μＦ／ｃｍ２ を越え
、しかもｔａｎδが２．５％未満という特性を得た。However, reduction and reoxidation type semiconductor ceramic capacitors have strong demands for various performance improvements, such as good temperature characteristics of capacitance, breakdown voltage of 400 V or more, large capacitance per unit area, and low dielectric loss. There has been a strong desire to develop a composition with even lower characteristics. The present inventors, in Japanese Patent Application No. 63-162568,
BaTiO3 -BaZrO3 -Bi2O3 -Ti
Cr, Fe, Co, Z in O2 or ZrO2-based solid solution
A ceramic composition for a reduction and reoxidation type semiconductor capacitor containing 0.001 to 1.00% by weight of at least one of n, Cu, Al, Si, and Mg oxides has a breakdown voltage of 400 V or more and an insulation resistance. 109 Ω or more,
Characteristics were obtained in which the capacitance per unit area exceeded 0.65 μF/cm 2 and tan δ was less than 2.5%.
【０００８】[0008]
【発明が解決しようとする課題】しかしながら、還元再
酸化型半導体コンデンサは、ＪＩＳ−Ｆレベルの静電容
量温度特性の範囲においては、小型、大容量で、破壊電
圧、絶縁抵抗の高いものは、実用化されているが、静電
容量、温度特性の良好な範囲において小型、大容量化し
た場合には、破壊電圧、絶縁抵抗が低いものとなってい
た。還元再酸化型半導体セラミックコンデンサにおいて
は、一般的に表面部の誘電体層が、コンデンサの容量、
容量の温度特性、絶縁抵抗、破壊電圧及び誘電損失に大
きな影響をもっている。[Problems to be Solved by the Invention] However, reduction and reoxidation semiconductor capacitors are small, large in capacity, and have high breakdown voltage and insulation resistance within the JIS-F level capacitance temperature characteristic range. Although it has been put into practical use, when it is made smaller and has a larger capacity within a range with good capacitance and temperature characteristics, the breakdown voltage and insulation resistance are low. In reduction and reoxidation type semiconductor ceramic capacitors, the dielectric layer on the surface generally increases the capacitance,
It has a large influence on the temperature characteristics of capacitance, insulation resistance, breakdown voltage, and dielectric loss.
【０００９】容量の温度特性の改善を行なうには、誘電
体層の誘電率の温度特性を平坦化する必要があり、Ｂｉ
２ Ｏ３ 等が添加剤として用いられている。この様な
添加剤の添加量を増加させることにより、容量の温度特
性の改善がなされるが、反面、誘電体層の誘電率は低下
してしまう。即ち、容量温度特性の良好な範囲において
小型、大容量化する場合には、誘電体層の誘電率が低い
ため、誘電体層を薄くする必要があり、結局、絶縁抵抗
及び破壊電圧が低下してしまう。In order to improve the temperature characteristics of the capacitance, it is necessary to flatten the temperature characteristics of the dielectric constant of the dielectric layer.
2 O3 etc. are used as additives. By increasing the amount of such additives added, the temperature characteristics of the capacitance can be improved, but on the other hand, the dielectric constant of the dielectric layer decreases. In other words, when increasing the size and capacity within a range with good capacitance-temperature characteristics, the dielectric layer has a low dielectric constant, so it is necessary to make the dielectric layer thinner, which results in a decrease in insulation resistance and breakdown voltage. It ends up.
【００１０】本発明の目的は、小型大容量で、且つ良好
な静電容量温度特性を有するコンデンサを得ることがで
きる。還元再酸化型半導体コンデンサ用セラミック組成
物を提供することにある。具体的には容量の温度特性が
±５５％以内、単位面積当たりの容量が０．６０μＦ／
ｃｍ２ 以上、絶縁抵抗１０１０Ω以上、破壊電圧７０
０Ｖ以上で、しかもｔａｎδが２．０％未満という特性
の還元再酸化型半導体コンデンサ用セラミック組成物を
提供することにある。[0010] An object of the present invention is to obtain a capacitor that is small in size, has a large capacity, and has good capacitance temperature characteristics. An object of the present invention is to provide a ceramic composition for a reduction and reoxidation type semiconductor capacitor. Specifically, the temperature characteristic of capacitance is within ±55%, and the capacitance per unit area is 0.60μF/
cm2 or more, insulation resistance 1010Ω or more, breakdown voltage 70
It is an object of the present invention to provide a ceramic composition for a reduction and reoxidation type semiconductor capacitor which has characteristics of 0 V or higher and tan δ of less than 2.0%.
【００１１】[0011]
【課題を解決するための手段】本発明者らは、前記の目
的で種々研究の結果、本発明を完成した。即ち本発明は
、
（イ）ＢａＺｒＯ３ ０〜２０モル％、ＳｒＴｉＯ
３ ０〜２０モル％、
ＢａＴｉＯ３ ４０〜１００％モル；（ロ）Ｂｉ２
Ｏ３ ；
（ハ）ＴｉＯ２ 又はＺｒＯ２ ；
（ニ）Ｌａ、Ｃｅ、Ｎｂ、Ｎｄ、Ｄｙ、Ｙ、Ｓｂ、Ｗ、
及びＴａの各酸化物の少なくとも一種；（ホ）Ｃｒ、Ｆ
ｅ、Ｃｏ、Ｚｎ、Ｃｕ、Ａｌ、Ｍｇ及びＳｉの各酸化物
の少なくとも一種；を実質的主成分として含有し、（イ
）成分、（ロ）成分、（ハ）成分、（ニ）成分はモル比
で１００：０．１〜２．５：０．１〜８．５：０．１〜
５．０であり、（ホ）成分は（イ）、（ロ）、（ハ）、
（ニ）の合計量の０．００１〜１．００重量％である還
元再酸化型半導体セラミックコンデンサ用組成物に関す
る。[Means for Solving the Problems] The present inventors completed the present invention as a result of various studies for the above-mentioned purpose. That is, the present invention includes (a) BaZrO3 0 to 20 mol%, SrTiO
3 0 to 20 mol%, BaTiO3 40 to 100% mol; (b) Bi2
O3; (c) TiO2 or ZrO2; (d) La, Ce, Nb, Nd, Dy, Y, Sb, W,
and at least one kind of each oxide of Ta; (e) Cr, F
Contains as a substantial main component at least one of the following oxides: e, Co, Zn, Cu, Al, Mg, and Si; Molar ratio: 100:0.1~2.5:0.1~8.5:0.1~
5.0, and (e) components are (a), (b), (c),
The present invention relates to a composition for a reduction and reoxidation type semiconductor ceramic capacitor in which the amount of (d) is 0.001 to 1.00% by weight based on the total amount.
【００１２】次に各成分について説明する。先ず（イ）
成分について説明する。ＢａＴｉＯ３ は周知のように
、この種の組成物の主成分である。本発明においては、
このＢａＴｉＯ３ の一部をＢａＺｒＯ３ 及び又はＳ
ｒＴｉＯ３ に置換することができる。２０モル％まで
をＢａＺｒＯ３ と置換することにより組成物の温度に
よる容量の変化を少なくすることができる。即ち容量の
温度特性を向上せしめる。添加量が２０モル％を越える
と、組成物のキュリー点が低くなりすぎるため、温度特
性が±５５％を越えてしまう。特に好ましい組成範囲は
０〜１５モル％である。Next, each component will be explained. First (a)
Let's explain the ingredients. BaTiO3 is, as is well known, the main component of this type of composition. In the present invention,
A part of this BaTiO3 is converted into BaZrO3 and/or S
It can be replaced with rTiO3. By replacing up to 20 mol% with BaZrO3, the change in capacity due to temperature of the composition can be reduced. In other words, the temperature characteristics of the capacitance are improved. If the amount added exceeds 20 mol%, the Curie point of the composition becomes too low, resulting in temperature characteristics exceeding ±55%. A particularly preferred composition range is 0 to 15 mol%.
【００１３】ＢａＴｉＯ３ の一部をＳｒＴｉＯ３ に
置換すると組成物のキュリー点（約１２０℃）は低下す
るがその量が多くなると、キュリー点が低下しすぎ、且
つ誘電率が低くなりすぎるので、単位面積当たりの容量
が小さくなる。即ち本発明の組成物においては、ＢａＴ
ｉＯ３ ２０モル％までをＳｒＴｉＯ３ と置換するこ
とができるものとした。特に好ましい組成範囲は０〜１
５モル％である。[0013] When a part of BaTiO3 is replaced with SrTiO3, the Curie point (approximately 120°C) of the composition is lowered, but if the amount is too large, the Curie point lowers too much and the dielectric constant becomes too low. The per unit capacity becomes smaller. That is, in the composition of the present invention, BaT
It was assumed that up to 20 mol% of iO3 could be replaced with SrTiO3. A particularly preferable composition range is 0 to 1
It is 5 mol%.
【００１４】前記（ロ）成分であるＢｉ２ Ｏ３ は誘
電体磁器の容量の温度特性の平坦化、及びキュリー点の
移動の効果がある。しかし（イ）成分に対してモル比で
０．１より少ない場合は効果を示さず、又モル比で２．
５を越えた場合は焼成の際の蒸発量が多くなり、その組
成物はセラミックコンデンサとしての使用に不適となる
。前記（ハ）成分であるＴｉＯ２ 又はＺｒＯ２ は誘
電体磁器の容量の温度特性の平坦化、還元温度の低下、
更に磁器自体の比抵抗の低下等の効果がある。その量が
前記（イ）成分に対してモル比で０．１より少ない場合
は効果がなく、又８．５を越えると誘電率が低下し、又
絶縁抵抗も低下する。Bi2 O3, which is the component (b), has the effect of flattening the temperature characteristics of the capacitance of the dielectric ceramic and moving the Curie point. However, if the molar ratio to component (a) is less than 0.1, no effect will be shown, and if the molar ratio is less than 2.
If it exceeds 5, the amount of evaporation during firing will increase, making the composition unsuitable for use as a ceramic capacitor. The component (c) TiO2 or ZrO2 flattens the temperature characteristics of the capacitance of the dielectric ceramic, lowers the reduction temperature,
Furthermore, there are effects such as a reduction in the specific resistance of the porcelain itself. If the amount is less than 0.1 in molar ratio with respect to component (a), there will be no effect, and if it exceeds 8.5, the dielectric constant and insulation resistance will decrease.
【００１５】（ニ）成分であるＬａ、Ｃｅ、Ｎｂ、Ｎｄ
、Ｄｙ、Ｙ、Ｓｂ、Ｗ及びＴａの各酸化物は、Ｂｉ２
Ｏ３ と同様、キュリー点の移動の効果がある。更に、
半導体の抵抗を減少させる効果をあわせ持つ。その量が
前記（イ）成分に対してモル比で０．１より少ない場合
は効果を示さず、又、５．０より多いと、キュリー点が
低くなりすぎると共に、半導体の抵抗が高くなり、単位
面積当たりの容量の低下と、誘電損失が高くなる。(d) Components La, Ce, Nb, Nd
, Dy, Y, Sb, W and Ta are Bi2
Similar to O3, it has the effect of shifting the Curie point. Furthermore,
It also has the effect of reducing the resistance of semiconductors. If the amount is less than 0.1 in molar ratio to the component (a), no effect will be shown, and if it is more than 5.0, the Curie point will become too low and the resistance of the semiconductor will increase. Capacity per unit area decreases and dielectric loss increases.
【００１６】本発明の組成物は、（ロ）成分であるＢｉ
２ Ｏ３と（ハ）成分であるＬａ、Ｃｅ、Ｎｂ、Ｎｄ、
Ｄｙ、Ｙ、Ｓｂ、Ｗ及びＴａの各酸化物の少なくとも一
種の両成分を含有していることに特徴がある。即ち、Ｂ
ｉ２ Ｏ３ はキュリー点の移動の効果はあるが誘電率
の低下を生じセラミックコンデンサとしての使用に不適
となる虞れがあるが、（ハ）成分であるＬａ等の酸化物
が共存するので、誘電率を低下させることなくキュリー
点の移動を行なうことが可能となるからである。[0016] The composition of the present invention comprises (b) component Bi.
2 O3 and (c) components La, Ce, Nb, Nd,
It is characterized by containing both components of at least one of the oxides of Dy, Y, Sb, W, and Ta. That is, B
Although i2O3 has the effect of shifting the Curie point, it lowers the dielectric constant and may become unsuitable for use as a ceramic capacitor. This is because it becomes possible to move the Curie point without reducing the rate.
【００１７】（ホ）成分であるＣｒ、Ｆｅ、Ｃｏ、Ｚｎ
、Ｃｕ、Ａｌ、Ｍｇ及びＳｉの各酸化物は、破壊電圧、
絶縁抵抗、単位面積当たりの容量を大幅に向上し、しか
もｔａｎδを極めて低い値とすることができる。
尚、添加量は実験の結果、好適の範囲は前記の（イ）、
（ロ）、（ハ）、（ニ）の合計組成に対して０．００１
〜１．００重量％、好ましくは０．００５〜０．８０重
量％であることを確認した。(e) Components Cr, Fe, Co, Zn
, Cu, Al, Mg and Si oxides have a breakdown voltage,
Insulation resistance and capacitance per unit area can be greatly improved, and tan δ can be made to an extremely low value. In addition, as a result of experiments, the suitable range for the addition amount is (a) above.
0.001 for the total composition of (b), (c), and (d)
It was confirmed that the amount was 1.00% by weight, preferably 0.005 to 0.80% by weight.
【００１８】この磁器組成物から還元再酸化型半導体磁
器コンデンサを製造するには、慣用の方法を用いれば足
りる。即ち、先ず前記範囲の組成物を空気中で１２００
〜１４００℃の温度に１〜４時間加熱し、焼結して絶縁
体磁器を製造する。次に、これを還元性ガス例えば水素
、一酸化炭素、アンモニア等の単独又は窒素ガス、アル
ゴン等の不活性ガスとの混合ガス流中で、９００〜１２
５０℃にて０．５〜１０時間処理して磁器を半導体化す
る。更に、空気中で７００〜１２００℃で０．２５〜５
時間処理することにより半導体磁器の表面部に薄い再酸
化層即ち誘電体層が形成される。次に、電極用の銀ペー
ストを塗布し焼き付けすることにより、還元再酸化型半
導体磁器セラミックコンデンサが完成する。A reduction and reoxidation type semiconductor ceramic capacitor can be manufactured from this ceramic composition by using a conventional method. That is, first, a composition in the above range was heated in air for 1200 min.
It is heated to a temperature of ~1400° C. for 1 to 4 hours and sintered to produce insulating porcelain. Next, this is heated in a flow of reducing gas such as hydrogen, carbon monoxide, ammonia, etc. alone or mixed with an inert gas such as nitrogen gas, argon, etc. to 900 to 12
The porcelain is converted into a semiconductor by processing at 50° C. for 0.5 to 10 hours. Furthermore, 0.25 to 5 at 700 to 1200℃ in air
By time treatment, a thin reoxidation layer, ie, a dielectric layer, is formed on the surface of the semiconductor ceramic. Next, a reduction and reoxidation semiconductor porcelain capacitor is completed by applying and baking a silver paste for electrodes.
【００１９】[0019]
【発明の効果】本発明の組成物は、従来の組成物に比し
コンデンサ用として優れた性質を有する。即ち、容量の
温度特性が±５５％以内、破壊電圧７００Ｖ以上、絶縁
抵抗１０１０Ω以上、単位面積当たりの容量が０．６０
μＦ／ｃｍ２ 以上と大きいにもかかわらず、ｔａｎδ
が２．０％未満と極めて優れた特性を同時に満足するも
のであり、これにより、他の性能を低下させることなく
高誘電率で低誘電損失を有する還元再酸化型半導体磁器
セラミックスコンデンサを提供することが可能となった
。Effects of the Invention The composition of the present invention has superior properties for use in capacitors as compared to conventional compositions. That is, the temperature characteristic of capacitance is within ±55%, the breakdown voltage is 700V or more, the insulation resistance is 1010Ω or more, and the capacitance per unit area is 0.60.
Despite being large, more than μF/cm2, tanδ
is less than 2.0%, which satisfies extremely excellent characteristics at the same time, thereby providing a reduction and reoxidation type semiconductor porcelain ceramic capacitor that has a high dielectric constant and low dielectric loss without deteriorating other performances. It became possible.
【００２０】実施例 １〜４５、比較例 １〜１２
市販の工業用原料ＢａＣＯ３ 粉末（純度９９．０％以
上）、ＳｒＣＯ３ 粉末（純度９９．０％以上）、Ｔｉ
Ｏ２ 粉末（純度９９．０％以上）、ＺｒＯ２ 粉末（
純度９９．０％以上）、Ｂｉ２Ｏ３ （純度９９．０％
以上）、市販の試薬特級Ｌａ２ Ｏ３ 、ＣｅＯ２ 、
Ｎｂ２ Ｏ５ 、Ｎｄ２ Ｏ３ 、Ｄｙ２ Ｏ３ 、Ｙ
２ Ｏ３ 、Ｓｂ２Ｏ３ 、ＷＯ３ 及びＴａ２ Ｏ５
の各粉末及び市販の試薬特級Ｃｒ２ Ｏ３ 、Ｆｅ２
Ｏ３ 、ＣｏＯ、ＺｎＯ、ＣｕＯ、Ａｌ２ Ｏ３ 、
ＳｉＯ２ 及びＭｇＯの各粉末を用い、表 １，表２に
示す本発明の組成物、即ち実施例、表３に示す本発明外
の組成物、即ち比較例の組成比になる用に配合し、ポッ
トとナイロンボールを用いて湿式混合した。乾燥後、各
混合物を１１５０℃の温度で４時間仮焼成した。この仮
焼物を湿式粉砕して、乾燥した後ポリビニールアルコー
ル水溶液をバインダーにして混合し、３２メッシュパス
に整粒した。この整粒物を直径９．５ｍｍ、厚さ０．５
ｍｍの円板形に約１ｔ／ｃｍ２ の圧力で成形し、これ
らの成形体を空気中において１３５０℃の温度で２時間
焼成して得た直径約８．０ｍｍ、厚さ約０．４ｍｍの円
板形誘電体磁器を９０％Ｎ２ −１０％Ｈ２ 混合ガス
気流中にて１０５０℃の温度で２時間加熱処理して半導
体化した。次にこの半導体磁器を空気中において１００
０℃の温度で１時間加熱処理した。このようにして得ら
れた還元再酸化型半導体磁器の両面に、銀電極を焼き付
けてコンデンサ素子とし、その単位面積当たりの容量Ｃ
、誘電損失ｔａｎδ（以上測定電圧；交流０．１Ｖ、周
波数；１ｋＨｚ）、絶縁抵抗ＩＲ（印加電圧；直流１０
Ｖ）、絶縁破壊電圧Ｖｂを測定した。その結果を実施例
の表１，２に対しては表４，５に、比較例の表３に対し
ては表６に示す。Examples 1 to 45, Comparative Examples 1 to 12
Commercially available industrial raw materials BaCO3 powder (purity 99.0% or higher), SrCO3 powder (purity 99.0% or higher), Ti
O2 powder (purity 99.0% or more), ZrO2 powder (
(purity 99.0% or more), Bi2O3 (purity 99.0% or more)
above), commercially available reagent special grade La2O3, CeO2,
Nb2O5, Nd2O3, Dy2O3, Y
2O3, Sb2O3, WO3 and Ta2O5
Each powder and commercially available reagent special grade Cr2O3, Fe2
O3, CoO, ZnO, CuO, Al2O3,
Using each powder of SiO2 and MgO, the compositions were blended to achieve the composition ratios of the composition of the present invention shown in Tables 1 and 2, that is, Examples, and the compositions other than the present invention shown in Table 3, that is, Comparative Examples, Wet mixing was performed using a pot and a nylon ball. After drying, each mixture was calcined at a temperature of 1150° C. for 4 hours. This calcined product was wet-pulverized, dried, mixed with an aqueous polyvinyl alcohol solution as a binder, and sized into a 32-mesh pass. This sized product has a diameter of 9.5 mm and a thickness of 0.5 mm.
A circle with a diameter of approximately 8.0 mm and a thickness of approximately 0.4 mm was obtained by molding the molded body into a disc shape of 1 mm at a pressure of approximately 1 t/cm2 and firing the molded body in air at a temperature of 1350°C for 2 hours. A plate-shaped dielectric ceramic was heat-treated at a temperature of 1050° C. for 2 hours in a 90% N 2 -10% H 2 mixed gas flow to convert it into a semiconductor. Next, this semiconductor porcelain was placed in the air for 100 min.
Heat treatment was performed at a temperature of 0° C. for 1 hour. Silver electrodes are baked on both sides of the reduced and reoxidized semiconductor porcelain obtained in this way to form a capacitor element, and its capacitance per unit area C
, dielectric loss tan δ (measured voltage: AC 0.1 V, frequency: 1 kHz), insulation resistance IR (applied voltage: DC 10
V) and dielectric breakdown voltage Vb were measured. The results are shown in Tables 4 and 5 for Tables 1 and 2 of Examples, and Table 6 for Table 3 of Comparative Examples.
【表１】[Table 1]
【表２】[Table 2]
【表３】[Table 3]
【表４】[Table 4]
【表５】[Table 5]
【表６】[Table 6]
【００２１】本発明に係る組成物は、表１，２，４，５
から明らかなように還元再酸化型半導体セラミックコン
デンサとして非常に優れた特性を有している。例えば、
実施例１３において、容量の温度特性が±５２％以内、
単位面積当りの容量が０．６１μＦ／ｃｍ２ と大きい
にもかかわらず、絶縁抵抗が４．１×１０１０Ωと極め
て大きく、更に破壊電圧Ｖｂ も７４０Ｖと大きく、誘
電損失ｔａｎδが１．５％と小さい。これに比較して、
Ｂｉ２ Ｏ３ の配合していない比較例３では、容量の
温度特性が±７５％以内で、誘電損失ｔａｎδが２．９
％と共に高く、単位面積当りの容量が０．４８μＦ／ｃ
ｍ２ と小さく、更に、絶縁抵抗が１．３×１０９ Ω
で、破壊電圧Ｖｂ が５７０Ｖと共に低かった。そして
、Ｂｉ２ Ｏ３ の配合量の多い比較例４では、容量の
温度特性が±４０％以内であったが、単位面積当りの容
量が０．４２μＦ／ｃｍ２ と小さく、誘電損失ｔａｎ
δが３．３％と高く、更に絶縁抵抗が２．５×１０９
Ωで、破壊電圧Ｖｂ も５４０Ｖと共に低かった。[0021] The composition according to the present invention is shown in Tables 1, 2, 4, and 5.
As is clear from the above, it has very excellent characteristics as a reduction-reoxidation type semiconductor ceramic capacitor. for example,
In Example 13, the temperature characteristic of capacity was within ±52%,
Although the capacitance per unit area is large at 0.61 μF/cm2, the insulation resistance is extremely high at 4.1×10 10 Ω, the breakdown voltage Vb is also large at 740 V, and the dielectric loss tan δ is small at 1.5%. Compared to this,
In Comparative Example 3, which does not contain Bi2O3, the capacitance temperature characteristics are within ±75% and the dielectric loss tanδ is 2.9.
%, and the capacitance per unit area is 0.48μF/c
m2, and insulation resistance is 1.3×109 Ω.
The breakdown voltage Vb was as low as 570V. In Comparative Example 4 with a large amount of Bi2O3, the temperature characteristics of the capacitance were within ±40%, but the capacitance per unit area was as small as 0.42 μF/cm2, and the dielectric loss tan
δ is high at 3.3%, and insulation resistance is 2.5×109
Ω, and the breakdown voltage Vb was also low at 540V.
【００２２】又、実施例２４では、容量の温度特性が±
５２％以内、単位面積当りの容量が０．６３μＦ／ｃｍ
２ と大きいにもかかわらず、絶縁抵抗が４．３×１０
１０Ωと極めて大きく、更に破壊電圧Ｖｂ も７５０Ｖ
と大きく、誘電損失ｔａｎδが１．８％と小さい。これ
に比較し、Ｌａ２ Ｏ３ 等を配合していない比較例９
については、容量の温度特性が±６５％以内、単位面積
当りの容量が、０．５０μＦ／ｃｍ２ であり、誘電損
失ｔａｎδが３．５％と高く、絶縁抵抗が２．２×１０
９ Ωと低く、破壊電圧Ｖｂ も５００Ｖと低かった。Further, in Example 24, the temperature characteristics of the capacitance are ±
Within 52%, capacitance per unit area is 0.63μF/cm
Although the insulation resistance is as large as 2, the insulation resistance is 4.3×10
It is extremely large at 10Ω, and the breakdown voltage Vb is also 750V.
The dielectric loss tan δ is as small as 1.8%. Compared to this, Comparative Example 9 does not contain La2O3 etc.
The temperature characteristics of the capacitance are within ±65%, the capacitance per unit area is 0.50μF/cm2, the dielectric loss tan δ is high at 3.5%, and the insulation resistance is 2.2×10
The resistance was as low as 9 Ω, and the breakdown voltage Vb was also as low as 500V.
Claims (1)
、ＳｒＴｉＯ３ ０〜２０モル％、ＢａＴｉＯ３
４０〜１００％モル； （ロ）Ｂｉ２ Ｏ３ ； （ハ）ＴｉＯ２ 又はＺｒＯ２ ； （ニ）Ｌａ、Ｃｅ、Ｎｂ、Ｎｄ、Ｄｙ、Ｙ、Ｓｂ、Ｗ、
及びＴａの各酸化物の少なくとも一種；（ホ）Ｃｒ、Ｆ
ｅ、Ｃｏ、Ｚｎ、Ｃｕ、Ａｌ、Ｍｇ及びＳｉの各酸化物
の少なくとも一種；を実質的主成分として含有し、（イ
）成分、（ロ）成分、（ハ）成分、（ニ）成分はモル比
で１００：０．１〜２．５：０．１〜８．５：０．１〜
５．０であり、（ホ）成分は（イ）、（ロ）、（ハ）、
（ニ）の合計量の０．００１〜１．００重量％である還
元再酸化型半導体セラミックコンデンサ用組成物。Claim 1: (a) BaZrO3 0 to 20 mol%
, SrTiO3 0-20 mol%, BaTiO3
40-100% mole; (b) Bi2 O3; (c) TiO2 or ZrO2; (d) La, Ce, Nb, Nd, Dy, Y, Sb, W,
and at least one kind of each oxide of Ta; (e) Cr, F
Contains as a substantial main component at least one of the following oxides: e, Co, Zn, Cu, Al, Mg, and Si; Molar ratio: 100:0.1~2.5:0.1~8.5:0.1~
5.0, and (e) components are (a), (b), (c),
A composition for a reduction and reoxidation type semiconductor ceramic capacitor that is 0.001 to 1.00% by weight of the total amount of (d).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3149206A JPH04349302A (en) | 1991-05-27 | 1991-05-27 | Compound for reduction oxidization type semiconductor ceramic condenser |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3149206A JPH04349302A (en) | 1991-05-27 | 1991-05-27 | Compound for reduction oxidization type semiconductor ceramic condenser |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04349302A true JPH04349302A (en) | 1992-12-03 |
Family
ID=15470151
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3149206A Pending JPH04349302A (en) | 1991-05-27 | 1991-05-27 | Compound for reduction oxidization type semiconductor ceramic condenser |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04349302A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001082311A1 (en) | 2000-04-26 | 2001-11-01 | The Furukawa Electric Co., Ltd. | Dielectric ceramic, resin-ceramics composite, and electric parts and antenna and method for their manufacture |
| JP2007153710A (en) * | 2005-12-07 | 2007-06-21 | Tdk Corp | Dielectric porcelain composition and electronic component |
| US11202007B1 (en) | 2019-09-27 | 2021-12-14 | Apple Inc. | Camera movement control for reduced power consumption |
-
1991
- 1991-05-27 JP JP3149206A patent/JPH04349302A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001082311A1 (en) | 2000-04-26 | 2001-11-01 | The Furukawa Electric Co., Ltd. | Dielectric ceramic, resin-ceramics composite, and electric parts and antenna and method for their manufacture |
| EP1205944A1 (en) * | 2000-04-26 | 2002-05-15 | The Furukawa Electric Co., Ltd. | Dielectric ceramic, resin-ceramics composite, and electric parts and antenna and method for their manufacture |
| EP1205944A4 (en) * | 2000-04-26 | 2007-03-07 | Furukawa Electric Co Ltd | Dielectric ceramic, resin-ceramics composite, and electric parts and antenna and method for their manufacture |
| JP2007153710A (en) * | 2005-12-07 | 2007-06-21 | Tdk Corp | Dielectric porcelain composition and electronic component |
| US11202007B1 (en) | 2019-09-27 | 2021-12-14 | Apple Inc. | Camera movement control for reduced power consumption |
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