JPS6248367B2 - - Google Patents
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- Publication number
- JPS6248367B2 JPS6248367B2 JP15640281A JP15640281A JPS6248367B2 JP S6248367 B2 JPS6248367 B2 JP S6248367B2 JP 15640281 A JP15640281 A JP 15640281A JP 15640281 A JP15640281 A JP 15640281A JP S6248367 B2 JPS6248367 B2 JP S6248367B2
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- sio
- semiconductor
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- 239000004065 semiconductor Substances 0.000 claims description 38
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 claims description 25
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 25
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 24
- 229910052573 porcelain Inorganic materials 0.000 claims description 20
- 239000000126 substance Substances 0.000 claims description 18
- 229910002367 SrTiO Inorganic materials 0.000 claims description 16
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims description 14
- 239000000919 ceramic Substances 0.000 claims description 14
- 239000003990 capacitor Substances 0.000 claims description 12
- 229910005793 GeO 2 Inorganic materials 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 4
- 239000003985 ceramic capacitor Substances 0.000 description 14
- 239000000203 mixture Substances 0.000 description 11
- 239000013078 crystal Substances 0.000 description 10
- 238000009792 diffusion process Methods 0.000 description 7
- 239000011810 insulating material Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- 208000006558 Dental Calculus Diseases 0.000 description 1
- 239000005041 Mylar™ Substances 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium 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
- 239000002131 composite material Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 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
- 238000010304 firing Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N lead(II) oxide Inorganic materials [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000010405 reoxidation reaction Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910000018 strontium carbonate Inorganic materials 0.000 description 1
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Landscapes
- Ceramic Capacitors (AREA)
- Inorganic Insulating Materials (AREA)
Description
本発明は、見掛け比誘電率が大きく、損失が低
く、誘電率の温度変化率が小さいチタン酸ストロ
ンチウム系の粒界層型（境界層型）半導体磁器コ
ンデンサの磁器及びその製造方法に関するもので
ある。
コンデンサの小型化の要求に応えるために、例
えば、BaTiO3系えん層容量型コンデンサ、
BaTiO3系還元再酸化型コンデンサ、BaTiO3粒界
絶縁型コンデンサSrTiO3系粒界層型コンデンサ
等が開発されている。これ等の内の１つの
SrTiO3系粒界層型半導体磁器コンデンサとし
て、特公昭55−25489号公報に示されている
SrTiO3，Nb2O3，GeO2から成る磁器の結晶粒界
にPbO，Bi2O3，B2O3を含有させてなる半導体磁
器は、BaTiO3系半導体磁器コンデンサとほぼ同
じ見掛け比誘電率55000〜65000を有し、且つ
SrTiO3常誘電体を使用しているため小型で損失
係数tanδが小さく且つ比誘電率の温度特性も良
好なコンデンサを提供することが出来る。従つ
て、この磁器コンデンサをマイラコンデンサの領
域に使用することが可能になり、磁器コンデンサ
の市場が一段と拡大された。しかし、アルミ電解
コンデンサ、タルタルコンデンサ等の代りに磁器
コンデンサを使用するために、見掛け比誘電率の
一層の向上が要求されている。
そこで、本発明の目的は、見掛け比誘電率の高
いSrTiO3系粒界層型半導体磁器コンデンサのた
めの磁器及びその製造方法を提供することにあ
る。
上記目的を達成するための本願の第１番目の発
明は、SrTiO390.68〜99.88重量％、Nb2O50.07〜
5.32重量％、及びGeO20.05〜4.00重量％で100重
量％となる組成の主成分100重量部と、副成分と
して、SiO2の重量部／Al2O3の重量部が1.5〜５と
なるように前記SiO20.02〜0.10重量部及び前記
Al2O30.01〜0.03重量部と、を含有し、且つ半導
体結晶粒界に、PbOとBi2O3とB2O3とから成る絶
縁化物質を、PbO11.0〜58重量％、Bi2O339.0〜
86.9重量％、B2O30.3〜3.5重量％で100重量％と
なる組成比で前記主成分と前記副成分との合計
100重量部に対して0.3〜５重量部含有しているこ
とを特徴とする半導体磁器コンデンサの半導体磁
器に係わるものである。
上記本発明によれば、主成分と、副成分と、絶
縁化物質とを特定された状態に含有させることに
より、tanδと抵抗率を良好に保つた状態で見掛
け比誘電率を増大させることが可能になり、例え
ば、見掛け比誘電率が約100000以上、tanδが１
％以下、抵抗率が1011Ω・cm以上の半導体磁器コ
ンデンサを提供することが可能になる。
本願の第２番目の発明は、上記半導体磁器を製
造する方法に係わるものであり、PbO，Bi2O3、
及びB2O3又はこれ等を得ることが出来る物質を
含むペーストを半導体磁器の表面に塗布し、拡散
することによつて半導体結晶粒界にPbO，
Bi2O3、及びB2O3を含有させることを特徴とする
ものである。この方法によれば、所望特性の半導
体磁器を容易に得ることが可能になる。
ところで、上記本発明は次の様な経緯によつて
完成した。一般に、粒界層型半導体磁器コンデン
サの場合、見掛けの比誘電率（εAPP）は、複雑
で半導体部の結晶粒子の大きさ（Gr）と粒界層
の厚み（Bt）と、粒界層に偏析する物質の比誘
電率（εｂ）とで決定され、次式で示される。
εAPP∝εｂ・Ｇｒ／Ｂｔ
従つて、見掛け比誘電率を大きくするには、半
導体部の結晶粒子を大きくすること、粒界層の厚
みを薄くすること、粒界層に偏析する物質の比誘
電率を大きくすることが重要である。本願出願人
等に係わる前述の特公昭55−25489号公報に示さ
れているSrTiO3系半導体磁器コンデンサでは、
粒界偏析物をBi2O3又はPbO―Bi2O3―B2O3系の
複合組成とすることによつて粒界層の比誘電率が
大きくなり、結果として性能良好なコンデンサが
得られた。又、SrTiO3系の半導体磁器の結晶粒
子を大きくする物質として、Nb2O5、GeO2の組
合せが良いことを示した。この時のSrTiO3系半
導体磁器の結晶粒子径は40〜60μｍである。尚こ
れ以上の大きさになるものもあるが、小さいもの
も混在し、結果として、40〜60μｍ程度の結晶粒
子に基づく見掛けの比誘電率しか得られない。そ
こで、結晶粒子を更に大きくすることについて
種々の実験及び検討を行つた。その中の１つとし
て、ボールミルで半導体磁器原料を混合する時に
磁器ボールミルから混入する微量のAl2O3、SiO2
がどのように影響するかを検討した。従来、ボー
ルミルで半導体磁器原料を混合する際に、メデイ
アの不純物としてAl2O3、SiO2が混入することは
知られており、これ等が合計で１重量％以下であ
れば特性上問題ないとされていた。しかし、本願
発明者が、ゴムライニングボールを用いてSiO2
とAl2O3のメデイアからの混入を阻止し、今迄不
純物として混入されていたAl2O3とSiO2と結晶粒
子との関係を調べたところ、主成物がSrTiO3と
Nb2O5とGeO2とから成り、絶縁化物質がPbOと
Bi2O3とB2O3とから成る半導体磁器に於いては、
Al2O3とSiO2との間に極めて重要な関係があるこ
とが判明した。即ち、SiO2／Al2O3の重量比が1.5
〜５となる範囲で且つ100重量部の主成分に対し
てSiO2を0.02〜0.10重量部、Al2O3を0.01〜0.03重
量部の範囲で付加すれば、tanδ及び抵抗率を良
好に保つた上で、半導体結晶粒子を大きくするた
めの添加物Nb2O5、GeO2の効果を増大させる働
きが生じ、平均結晶粒径が60〜120μｍになるこ
とが判つた。
以下、実施例について述べる。
実施例 １
工業用のSrTiO3（不純物として、Ba、Fe、
Mn、Ca、Na、Ｋ等を微量含有）、Nb2O5、
GeO2、SiO2及びAl2O3を第１表に示す組成となる
ように配合し、これ等に不純物が混入することを
防止するためにゴムライニングボール使用のゴム
ライニングミルで湿式混合をし、乾燥した後、ポ
リビニルアルコールのような公知のバインダを加
え、加圧成形機にて円板状に成形し、1000℃１時
間の熱処理によりバインダを除去した後、99％
N2―１％H2の弱還元性の雰囲気中において、
1350〜1450℃、２〜４時間焼結し、大きさがそれ
ぞれ直径約８mm、厚さ約0.4mmの円板状半導体磁
器を作製した。
次に、これらの円板状半導体磁器の片主面に
PbO粉末50重量％、Bi2O3粉末45重量％、B2O3粉
末５重量％で100重量％となるように配合された
絶縁化物質に有機バインダとしてニトロセルロー
ス及びブチルカルビトールを加えてペーストを作
製し、これを半導体磁器（重量約100mg）に対し
て10重量％（10mg）、スクリーン印刷で塗布し、
酸化雰囲気中で1150〜1300℃の範囲の一定温度で
２時間焼成し、半導体磁器粒界層に拡散し、この
粒界層を絶縁体化した。尚、ペーストの配合を絶
縁化物質約80重量％、有機バインダ約10重量％、
溶媒約10重量％とした。これにより、第１図に模
式的に示す半導体結晶粒子１と絶縁化された粒界
層２とから成る半導体磁器３が完成した。しかる
後、この半導体磁器３の両主面に銀ペーストを塗
布し、焼付けることによつて一対のコンデンサ電
極４，５を形成し、半導体磁器コンデンサとし
た。尚上記ペースト中のPbO、Bi2O3及びB2O3は
上記焼成時における蒸発等のために半導体磁器中
に全部拡散せず、一部のみが拡散する。即ち、各
成分の拡散量は半導体磁器の組成によつて異な
り、本実施例の組成の磁器に於ける塗布量に対す
る拡散量の割合は、PbOで6.16〜14.36％の範
囲、Bi2O3で12.82〜29.91％の範囲、B2O3で3.0〜
7.2％の範囲である。従つて、磁器中に於ける各
成分の拡散量は、100重量部の磁器に対して、
PbOが0.308〜0.718重量部、Bi2O3が0.577〜1.346
重量部、B2O3が0.015〜0.036重量部となる。そし
て、100重量部の磁器に対するPbOとBi2O3と
B2O3の合計拡散量は0.9〜2.1重量部となる。
このようにして得られた各試料について、見掛
けの比誘電率ε、誘電体損失tanδ、抵抗率ρを
測定したところ、第１表に示す結果が得られた。
尚、εとtanδは1kHzで測定し、ρは直流50Vを
印加して１分間経過した後に測定した。
第１表に於いて、主成分のSrTiO3とNb2O5と
GeO2との重量％の総和が100重量％である。また
副成分のSiO2とAl2O3とは、主成分100重量部に
対する重量部で示されている。
The present invention relates to a strontium titanate-based grain boundary layer type (boundary layer type) semiconductor ceramic capacitor having a large apparent relative permittivity, low loss, and a small rate of temperature change in permittivity, and a method for manufacturing the same. . In order to meet the demand for smaller capacitors, for example, BaTiO 3 -based layered capacitors,
BaTiO 3 -based reduction-reoxidation capacitors, BaTiO 3- grain boundary insulation capacitors, SrTiO 3 -based grain boundary layer capacitors, etc. have been developed. one of these
A SrTiO 3 grain boundary layer semiconductor ceramic capacitor is disclosed in Japanese Patent Publication No. 55-25489.
Semiconductor ceramics made of SrTiO 3 , Nb 2 O 3 , and GeO 2 containing PbO, Bi 2 O 3 , and B 2 O 3 in the grain boundaries have approximately the same apparent relative permittivity as BaTiO 3 -based semiconductor ceramic capacitors. has a rate of 55,000~65,000, and
Since SrTiO 3 paraelectric material is used, it is possible to provide a capacitor that is small, has a small loss coefficient tan δ, and has good temperature characteristics of dielectric constant. Therefore, it has become possible to use this ceramic capacitor in the field of Mylar capacitors, and the market for ceramic capacitors has further expanded. However, in order to use ceramic capacitors instead of aluminum electrolytic capacitors, tartar capacitors, etc., a further improvement in the apparent dielectric constant is required. SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a ceramic for an SrTiO 3 -based grain boundary layer type semiconductor ceramic capacitor having a high apparent dielectric constant, and a method for manufacturing the same. The first invention of the present application to achieve the above object includes SrTiO 3 90.68 to 99.88% by weight and Nb 2 O 5 0.07 to 99.88% by weight.
5.32% by weight, and 100% by weight of GeO 2 0.05 to 4.00% by weight as the main component, and as subcomponents, parts by weight of SiO 2 / parts by weight of Al 2 O 3 are 1.5 to 5. 0.02-0.10 parts by weight of SiO 2 and so on
0.01 to 0.03 parts by weight of Al 2 O 3 and an insulating substance consisting of PbO, Bi 2 O 3 and B 2 O 3 at the semiconductor grain boundaries, 11.0 to 58 parts by weight of PbO, 11.0 to 58 parts by weight of Bi 2 O 3 39.0～
The total of the main component and the subcomponent at a composition ratio of 86.9% by weight and 100% by weight with B 2 O 3 0.3 to 3.5% by weight.
This invention relates to a semiconductor ceramic of a semiconductor ceramic capacitor, characterized in that the content is 0.3 to 5 parts by weight per 100 parts by weight. According to the present invention, by containing the main component, the subcomponent, and the insulating substance in a specified state, it is possible to increase the apparent dielectric constant while maintaining good tan δ and resistivity. For example, when the apparent dielectric constant is approximately 100,000 or more and the tan δ is 1,
% or less, it becomes possible to provide a semiconductor ceramic capacitor with a resistivity of 10 11 Ω·cm or more. The second invention of the present application relates to a method of manufacturing the above-mentioned semiconductor porcelain, in which PbO, Bi 2 O 3 ,
A paste containing PbO, B 2 O 3 , or a substance capable of obtaining these is applied to the surface of the semiconductor ceramic and diffused to form PbO, PbO, and B 2 O 3 at the semiconductor grain boundaries.
It is characterized by containing Bi 2 O 3 and B 2 O 3 . According to this method, it becomes possible to easily obtain semiconductor ceramics with desired characteristics. By the way, the above-mentioned present invention was completed through the following circumstances. In general, in the case of grain boundary layer type semiconductor ceramic capacitors, the apparent dielectric constant (ε APP ) is complex and depends on the size of crystal grains in the semiconductor part (Gr), the thickness of the grain boundary layer (Bt), and the grain boundary layer. It is determined by the dielectric constant (εb) of the substance segregated in ε APP ∝εb・Gr/Bt Therefore, in order to increase the apparent relative permittivity, it is necessary to increase the size of the crystal grains in the semiconductor part, to reduce the thickness of the grain boundary layer, and to increase the ratio of substances segregated in the grain boundary layer. It is important to increase the dielectric constant. In the SrTiO 3 semiconductor ceramic capacitor disclosed in the above-mentioned Japanese Patent Publication No. 55-25489 filed by the applicant of the present application,
By making the grain boundary segregated material have a composite composition of Bi 2 O 3 or PbO-Bi 2 O 3 -B 2 O 3 system, the relative permittivity of the grain boundary layer increases, and as a result, a capacitor with good performance can be obtained. It was done. Furthermore, it was shown that the combination of Nb 2 O 5 and GeO 2 is good as a substance for enlarging the crystal grains of SrTiO 3 -based semiconductor ceramics. The crystal grain size of the SrTiO 3 semiconductor ceramic at this time is 40 to 60 μm. Although some particles have a larger size, there are also smaller particles, and as a result, only an apparent dielectric constant based on crystal grains of about 40 to 60 μm can be obtained. Therefore, various experiments and studies were conducted to make the crystal grains even larger. One of them is trace amounts of Al 2 O 3 and SiO 2 mixed in from the porcelain ball mill when mixing semiconductor porcelain raw materials in the ball mill.
We considered how this would be affected. Conventionally, when mixing semiconductor porcelain raw materials in a ball mill, it is known that Al 2 O 3 and SiO 2 are mixed in as impurities in the media, and as long as these are 1% by weight or less in total, there is no problem in terms of properties. It was said that However, the inventor of the present application has developed SiO 2 using a rubber-lined ball.
When we investigated the relationship between Al 2 O 3 , SiO 2 , and crystal particles that had been mixed as impurities until now, we found that the main constituents were SrTiO 3 and Al 2 O 3 from the media.
It consists of Nb 2 O 5 and GeO 2 , and the insulating material is PbO.
In semiconductor porcelain made of Bi 2 O 3 and B 2 O 3 ,
It has been found that there is a very important relationship between Al 2 O 3 and SiO 2 . That is, the weight ratio of SiO 2 /Al 2 O 3 is 1.5.
If SiO 2 is added in the range of 0.02 to 0.10 parts by weight and Al 2 O 3 is added in the range of 0.01 to 0.03 parts by weight to 100 parts by weight of the main component, tan δ and resistivity can be kept good. In addition, it was found that the effect of the additives Nb 2 O 5 and GeO 2 for enlarging semiconductor crystal grains was increased, and the average crystal grain size became 60 to 120 μm. Examples will be described below. Example 1 Industrial SrTiO 3 (contains Ba, Fe,
Contains trace amounts of Mn, Ca, Na, K, etc.), Nb 2 O 5 ,
GeO 2 , SiO 2 and Al 2 O 3 were blended to have the composition shown in Table 1, and wet mixed in a rubber-lined mill using rubber-lined balls to prevent impurities from being mixed in. After drying, add a known binder such as polyvinyl alcohol, mold into a disk shape with a pressure molding machine, remove the binder by heat treatment at 1000°C for 1 hour, and then 99%
In a weakly reducing atmosphere of N 2 -1% H 2 ,
Sintering was performed at 1350 to 1450°C for 2 to 4 hours to produce disk-shaped semiconductor porcelains each having a diameter of about 8 mm and a thickness of about 0.4 mm. Next, on one main surface of these disk-shaped semiconductor porcelains,
Nitrocellulose and butyl carbitol were added as organic binders to an insulating material blended to make 100% by weight of 50% by weight PbO powder, 45% by weight Bi 2 O 3 powder, and 5% by weight B 2 O 3 powder. A paste was prepared, and 10% by weight (10mg) of this was applied to semiconductor porcelain (weight approximately 100mg) by screen printing.
It was fired in an oxidizing atmosphere at a constant temperature in the range of 1150 to 1300° C. for 2 hours to diffuse into the grain boundary layer of the semiconductor porcelain, thereby converting this grain boundary layer into an insulator. The paste composition is approximately 80% by weight of insulating material, approximately 10% by weight of organic binder,
The solvent was approximately 10% by weight. As a result, a semiconductor ceramic 3 consisting of semiconductor crystal grains 1 and insulated grain boundary layers 2 schematically shown in FIG. 1 was completed. Thereafter, a pair of capacitor electrodes 4 and 5 were formed by applying silver paste to both main surfaces of this semiconductor ceramic 3 and baking it, thereby producing a semiconductor ceramic capacitor. Note that PbO, Bi 2 O 3 and B 2 O 3 in the paste do not all diffuse into the semiconductor porcelain due to evaporation during the firing, but only a portion thereof. That is, the amount of diffusion of each component differs depending on the composition of the semiconductor porcelain, and the ratio of the amount of diffusion to the amount of coating in the porcelain with the composition of this example is in the range of 6.16 to 14.36% for PbO, and in the range of 6.16 to 14.36% for Bi 2 O 3 . Range from 12.82 to 29.91%, from 3.0 to B2O3
It is in the range of 7.2%. Therefore, the amount of diffusion of each component in porcelain is:
PbO 0.308-0.718 parts by weight, Bi2O3 0.577-1.346
Part by weight, B 2 O 3 is 0.015 to 0.036 part by weight. and PbO and Bi2O3 for 100 parts by weight of porcelain .
The total amount of B 2 O 3 diffused is 0.9 to 2.1 parts by weight. When the apparent dielectric constant ε, dielectric loss tan δ, and resistivity ρ of each sample thus obtained were measured, the results shown in Table 1 were obtained.
Note that ε and tan δ were measured at 1 kHz, and ρ was measured after 1 minute had elapsed after applying 50 V DC. In Table 1, the main components SrTiO 3 and Nb 2 O 5
The total weight percentage with GeO 2 is 100 weight percent. Further, the subcomponents SiO 2 and Al 2 O 3 are shown in parts by weight relative to 100 parts by weight of the main component.
【表】【table】
【表】【table】
【表】
第１表から明らかなように、本発明で特定され
ている範囲に入る組成比を有する試料番号７，
８，10〜19，21〜32，34〜36，38〜42の磁器によ
れば、εが77000〜153000、tanδが0.4〜0.8％ρ
が１〜２×1011Ω・cmとなる。一方、本発明の範
囲外である試料番号１〜６，９，20，33，37，43
〜48の磁器から明らかなように、SiO2／Al2O3の
重量比が1.5未満範囲では80000以上のεを得るこ
とが出来ず、また上記比が５を越えた範囲では、
tanδ又はρが悪くなる。また、SiO2が100重量部
の主成分に対して0.02重量部未満であるとεを
80000以上にすることが出来ず、またこれが0.1重
量部を越すと、大きなεが得られなくなる。また
Al2O3が0.01重量部末満であると、80000以上のε
を得ることが不可能になり、これが0.03重量部を
越えると、εが80000以下になる。従つて、SiO2
及びAl2O3の好ましい範囲は、SiO2／Al2O3の重
量比が1.5〜５であると共に、SiO2が0.02〜0.1〜
重量部、Al2O3が0.01〜0.03重量部の範囲であ
る。
尚本発明の範囲内の試料の比誘電率εの温度特
性は第２図に示されるように、20℃の比誘電率を
基準にし、−25℃〜＋85℃の範囲において負の温
度側で＋15％以内の斜線領域、正の温度側で−15
％以内の斜線領域にすべての試料のものが入つ
た。
実施例 ２
実施例１に於けるペーストの絶縁化物質（拡散
物質）としてのPbO、Bi2O3、B2O3の比率のみを
第２表に示すように変化させ、製造方法は実施例
１と同一として磁器コンデンサを作製し、電気的
特性を測定したところ、第２表に示す結果が得ら
れた。[Table] As is clear from Table 1, sample number 7, which has a composition ratio within the range specified in the present invention,
According to the porcelains No. 8, 10-19, 21-32, 34-36, 38-42, ε is 77000-153000 and tanδ is 0.4-0.8% ρ.
is 1 to 2×10 11 Ω・cm. On the other hand, sample numbers 1 to 6, 9, 20, 33, 37, and 43 which are outside the scope of the present invention
As is clear from porcelain No. 48, it is not possible to obtain an ε of 80,000 or more when the weight ratio of SiO 2 /Al 2 O 3 is less than 1.5, and when the ratio exceeds 5,
tan δ or ρ becomes worse. In addition, if SiO 2 is less than 0.02 parts by weight based on 100 parts by weight of the main component, ε
If it cannot be made more than 80,000, and if it exceeds 0.1 parts by weight, it will not be possible to obtain a large ε. Also
When Al 2 O 3 is less than 0.01 parts by weight, ε of 80000 or more
If it exceeds 0.03 part by weight, ε becomes 80,000 or less. Therefore, SiO 2
The preferable range of Al 2 O 3 is that the weight ratio of SiO 2 /Al 2 O 3 is 1.5 to 5, and the SiO 2 is 0.02 to 0.1.
Parts by weight, Al2O3 ranges from 0.01 to 0.03 parts by weight. As shown in Figure 2, the temperature characteristics of the relative permittivity ε of the samples within the scope of the present invention are based on the relative permittivity of 20°C, and on the negative temperature side in the range of -25°C to +85°C. Shaded area within +15%, -15 on the positive temperature side
All samples fell within the shaded area within %. Example 2 Only the ratios of PbO, Bi 2 O 3 and B 2 O 3 as insulating substances (diffusion substances) of the paste in Example 1 were changed as shown in Table 2, and the manufacturing method was the same as that of Example 2. A ceramic capacitor was prepared in the same manner as in Example 1, and its electrical characteristics were measured, and the results shown in Table 2 were obtained.
【表】【table】
【表】
この第２表の試料番号49，52，54〜57，59，62
〜66，69，71〜73，75，77〜79から明らかなよう
に、PbOが32〜61重量％、Bi2O334〜64重量％、
B2O3が２〜10重量％の範囲では大きなεを有
し、tanδ及びρも優れている磁器を得ることが
出来る。一方、本発明の範囲外である試料番号
50，51，53，58，60，61，67，68，70，74，76か
ら明らかなように、PbO、Bi2O3、B2O3の比が本
発明の範囲外となれば所望の特性を得ることが不
可能になる。従つて、絶縁化物質の好ましい組成
比は、PbOが32〜61重量％、Bi2O3が34〜64重量
％、B2O3が２〜10重量％である。
また、絶縁化物質の塗布量及び加熱温度及び加
熱時間等を種々変えることによつて、絶縁化物質
の拡散量の異なる磁器を作製し、所望特性が得ら
れる磁器に於ける絶縁化物質の拡散量を求めたと
ころ、磁器100重量部に対して0.3〜５重量部であ
つた。そして、絶縁化物質の組成比の範囲は、
PbO11〜58重量％、Bi2O339〜86.9重量％、
B2O30.3〜3.5重量％であつた。絶縁化物質が0.3
重量部未満の場合及び５重量部を越える場合のい
ずれに於いても所望の特性を得ることが困難にな
る。
以上、本発明の実施例について述べたが、本発
明はこれに限定されるものではなく、更に変形可
能なものである。例えば、本発明の特徴を阻害し
ない範囲で他の特性改善物質を付加しても差支え
ない。また、PbO、Bi2O3、B2O3の粉末にてペー
ストを作製せずに、絶縁化のための拡散加熱で
PbO、Bi2O3、B2O3に変換される物質を磁器の一
方又は両方の主面に塗布して、最終的に磁器の中
にPbO、Bi2O3、B2O3を偏在させてもよい。ま
た、PbO、Bi2O3、B2O3に変換することが出来る
物質の配合物を作り、これを例えば1000℃で焼成
し、PbO―Bi2O3―B2O3の組成物を作り、これを
粉砕した粉末でペーストを作つて塗布してもよ
い。また、最初の原料をSrTiO3、Nb2O5、
GeO2、SiO2、Al2O3、PbO、Bi2O3、B2O3等とせ
ずに、これ等を得るための物質を原料としてもよ
い。例えばSrTiO3を炭酸ストロンチウムと酸化
チタンとから得るようにしてもよい。またゴムラ
イニングボールに限らずに、SiO2とAl2O3とが不
純絶物として混入する恐れのない他の容器を使用
して主成分と副成分との原料を混合するようにし
てもよい。[Table] Sample numbers 49, 52, 54 to 57, 59, 62 in this second table
As is clear from ~66, 69, 71-73, 75, 77-79, PbO is 32-61% by weight, Bi 2 O 3 34-64% by weight,
When B 2 O 3 is in the range of 2 to 10% by weight, it is possible to obtain porcelain having a large ε and excellent tan δ and ρ. On the other hand, sample numbers that are outside the scope of the present invention
50, 51, 53, 58, 60, 61, 67, 68, 70, 74, 76, if the ratio of PbO, Bi 2 O 3 and B 2 O 3 is outside the range of the present invention, the desired It becomes impossible to obtain the characteristics of Therefore, the preferred composition ratio of the insulating material is 32 to 61% by weight of PbO, 34 to 64% by weight of Bi2O3 , and 2 to 10% by weight of B2O3 . In addition, by varying the coating amount of the insulating substance, the heating temperature, the heating time, etc., porcelain with different amounts of diffusion of the insulating substance was produced, and the diffusion of the insulating substance in the porcelain to obtain the desired characteristics was investigated. When the amount was determined, it was 0.3 to 5 parts by weight per 100 parts by weight of porcelain. The composition ratio range of the insulating material is
PbO 11~58 wt%, Bi2O3 39 ~86.9 wt%,
B2O3 was 0.3-3.5 % by weight. Insulating material is 0.3
If the amount is less than 5 parts by weight or exceeds 5 parts by weight, it becomes difficult to obtain desired properties. Although the embodiments of the present invention have been described above, the present invention is not limited thereto and can be further modified. For example, other property-improving substances may be added as long as the characteristics of the present invention are not impaired. In addition, without making a paste using powders of PbO, Bi 2 O 3 and B 2 O 3 , diffusion heating for insulation can be used.
Substances that convert into PbO, Bi 2 O 3 , and B 2 O 3 are applied to one or both main surfaces of the porcelain, and finally PbO, Bi 2 O 3 , and B 2 O 3 are unevenly distributed in the porcelain. You may let them. In addition, a mixture of substances that can be converted into PbO, Bi 2 O 3 and B 2 O 3 is made, and this is fired at, for example, 1000°C to form a composition of PbO-Bi 2 O 3 -B 2 O 3 . You can also make a paste by grinding it into powder and apply it. In addition, the initial raw materials were SrTiO 3 , Nb 2 O 5 ,
Instead of using GeO 2 , SiO 2 , Al 2 O 3 , PbO, Bi 2 O 3 , B 2 O 3 , etc., substances for obtaining these may be used as raw materials. For example, SrTiO 3 may be obtained from strontium carbonate and titanium oxide. In addition, the raw materials for the main component and the subcomponent may be mixed using not only the rubber-lined ball but also other containers that are free from the risk of contamination with SiO 2 and Al 2 O 3 as impurities. .
第１図は本発明の実施例に係わる磁器コンデン
サを模式的に示す断面図、第２図は温度変化に対
する比誘電率の変化率を示す特性図である。
尚図面に用いられている符号に於いて、１は粒
子、２は粒界層、３は磁器、４，５は電極であ
る。
FIG. 1 is a cross-sectional view schematically showing a ceramic capacitor according to an embodiment of the present invention, and FIG. 2 is a characteristic diagram showing the rate of change in dielectric constant with respect to temperature change. In the symbols used in the drawings, 1 is a particle, 2 is a grain boundary layer, 3 is a ceramic, and 4 and 5 are electrodes.
Claims (1)
5.32重量％とGeO20.05〜4.00重量％とで100重量
％となる主成分100重量部、 SiO2 0.02〜0.10重量部、 Al2O3 0.01〜0.03重量部、 （但し、前記SiO2の重量部及び前記Al2O3の重
量部は、SiO2の重量部／Al2O3の重量部が1.5〜
5.0となる範囲内である） を有し、更に、PbO11.0〜58重量％とBi2O339.0
〜86.9重量％とB2O30.3〜3.5重量％とで100重量
％になる比率で前記PbOと前記Bi2O3と前記B2O3
とを含有し、前記PbOと前記Bi2O3と前記B2O3と
の合計重量部が前記主成成分と前記SiO2と前記
Al2O3との合計100重量部に対して0.3〜５重量部
とされていることを特徴とするコンデンサ用半導
体磁器。 ２ SrTiO390.68〜99.68重量％とNb2O50.07〜
5.32重量％とGeO20.05〜4.00重量％とで100重量
％となる主成分100重量部、 SiO2 0.02〜0.10重量部、 Al2O3 0.01〜0.03重量部、 （但し、前記SiO2の重量部及び前記Al2O3の重
量部は、SiO2の重量部／Al2O3の重量部が1.5〜
5.0となる範囲内である） から成る半導体磁器を作製する工程と、 前記半導体磁器の少なくとも一方の主面にPbO
又は加熱処理によつてPbOになる物質と、Bi2O3
又は加熱処理によつてBi2O3になる物質と、B2O3
又は加熱処理によつてB2O3になる物質とをPbO
に換算して32〜61重量％、Bi2O3に換算して34〜
64重量％、B2O3に換算して２〜10重量％で100重
量％となるような比で含むペーストを、前記半導
体磁器100重量部に対して１〜15重量部塗布し、
しかる後加熱処理することによつて前記半導体磁
器の結晶粒界にPbO，Bi2O3、及びB2O3を拡散さ
せる工程と、 を含む半導体磁器の製造方法。[Claims] 1 SrTiO 3 90.68 to 99.68 parts by weight and Nb 2 O 5 0.07 to
100 parts by weight of the main components, 100 parts by weight of 5.32% by weight and 0.05-4.00% by weight of GeO 2 , 0.02-0.10 parts by weight of SiO 2 , 0.01-0.03 parts by weight of Al 2 O 3 , (However, the weight of the above SiO 2 parts and the above-mentioned parts by weight of Al 2 O 3 are 1.5 to 1.5 parts by weight of SiO 2 / parts by weight of Al 2 O 3
5.0), and furthermore, PbO 11.0 to 58% by weight and Bi 2 O 3 39.0
The PbO, the Bi2O3 , and the B2O3 in a ratio of ~86.9% by weight and 0.3 to 3.5% by weight of B2O3 to 100% by weight .
and the total weight part of the PbO, the Bi 2 O 3 and the B 2 O 3 is the main component, the SiO 2 and the B 2 O 3.
A semiconductor ceramic for a capacitor, characterized in that the amount is 0.3 to 5 parts by weight per 100 parts by weight in total with Al 2 O 3 . 2 SrTiO 3 90.68~99.68% by weight and Nb 2 O 5 0.07~
100 parts by weight of the main components, 100 parts by weight of 5.32% by weight and 0.05-4.00% by weight of GeO 2 , 0.02-0.10 parts by weight of SiO 2 , 0.01-0.03 parts by weight of Al 2 O 3 , (However, the weight of the above SiO 2 parts and the above-mentioned parts by weight of Al 2 O 3 are 1.5 to 1.5 parts by weight of SiO 2 / parts by weight of Al 2 O 3
5.0); and PbO on at least one main surface of the semiconductor ceramic.
Or a substance that becomes PbO through heat treatment and Bi 2 O 3
Or a substance that becomes Bi 2 O 3 through heat treatment, and B 2 O 3
Or PbO with a substance that becomes B 2 O 3 through heat treatment.
32-61% by weight in terms of Bi2O3 , 34-61% in terms of Bi2O3
Applying 1 to 15 parts by weight of a paste containing 64% by weight, 2 to 10% by weight in terms of B 2 O 3 and 100 parts by weight to 100 parts by weight of the semiconductor porcelain,
A method for manufacturing semiconductor ceramics, comprising the steps of: diffusing PbO, Bi 2 O 3 and B 2 O 3 into the grain boundaries of the semiconductor ceramics through subsequent heat treatment.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15640281A JPS5857722A (en) | 1981-10-01 | 1981-10-01 | Semiconductor porcelain for semiconductor porcelain condenser and method of producing same |
| EP82108979A EP0076456B1 (en) | 1981-10-01 | 1982-09-28 | Dielectric ceramic materials with insulated boundaries between crystal grains, and process for preparation |
| DE8282108979T DE3274734D1 (en) | 1981-10-01 | 1982-09-28 | Dielectric ceramic materials with insulated boundaries between crystal grains, and process for preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15640281A JPS5857722A (en) | 1981-10-01 | 1981-10-01 | Semiconductor porcelain for semiconductor porcelain condenser and method of producing same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5857722A JPS5857722A (en) | 1983-04-06 |
| JPS6248367B2 true JPS6248367B2 (en) | 1987-10-13 |
Family
ID=15626949
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15640281A Granted JPS5857722A (en) | 1981-10-01 | 1981-10-01 | Semiconductor porcelain for semiconductor porcelain condenser and method of producing same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5857722A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63199895U (en) * | 1987-06-13 | 1988-12-22 |
-
1981
- 1981-10-01 JP JP15640281A patent/JPS5857722A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63199895U (en) * | 1987-06-13 | 1988-12-22 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5857722A (en) | 1983-04-06 |
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