JPH0154848B2 - - Google Patents
Info
- Publication number
- JPH0154848B2 JPH0154848B2 JP10466180A JP10466180A JPH0154848B2 JP H0154848 B2 JPH0154848 B2 JP H0154848B2 JP 10466180 A JP10466180 A JP 10466180A JP 10466180 A JP10466180 A JP 10466180A JP H0154848 B2 JPH0154848 B2 JP H0154848B2
- Authority
- JP
- Japan
- Prior art keywords
- grain boundary
- electrodes
- grain
- insulated semiconductor
- semiconductor
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 239000004065 semiconductor Substances 0.000 claims description 31
- 239000003990 capacitor Substances 0.000 claims description 20
- 239000003795 chemical substances by application Substances 0.000 claims description 17
- 229910052573 porcelain Inorganic materials 0.000 claims description 12
- 238000007772 electroless plating Methods 0.000 claims description 9
- 238000007747 plating Methods 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 239000010949 copper Substances 0.000 claims description 7
- 239000011521 glass Substances 0.000 claims description 6
- 229910052796 boron Inorganic materials 0.000 claims description 5
- 229910052797 bismuth Inorganic materials 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 9
- 238000009413 insulation Methods 0.000 description 9
- 229910052709 silver Inorganic materials 0.000 description 9
- 239000004332 silver Substances 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- 229910002367 SrTiO Inorganic materials 0.000 description 5
- 229910052745 lead Inorganic materials 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 229910008423 Si—B Inorganic materials 0.000 description 2
- 239000005388 borosilicate glass Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000003985 ceramic capacitor Substances 0.000 description 2
- 229910006339 Si—Pb Inorganic materials 0.000 description 1
- 229910052776 Thorium Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000005324 grain boundary diffusion Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000010405 reoxidation reaction Methods 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
Landscapes
- Ceramic Capacitors (AREA)
Description
本発明はチタン酸ストロンチウム（以下
SrTiO3という）を主成分とする粒界絶縁型半導
体コンデンサの電極を改良したもので、従来の銀
電極を形成した粒界絶縁型半導体コンデンサと同
等あるいは遜色のない電気特性および信頼性をも
ち、かつ安価なメツキ電極を有する粒界絶縁型半
導体コンデンサ製造方法を提供するものである。
SrTiO3を主成分とする粒界絶縁型半導体コン
デンサは、温度特性、DCバイアスなどに優れ、
かつ比誘電率も極めて大きいため、小型大容量の
優れた半導体コンデンサとして低電圧電子回路に
多く使用されている。
しかしこの粒界絶縁型半導体コンデンサの電極
は従来のセラミツクコンデンサ、再酸化型半導体
コンデンサと同様に銀を主成分とする電極が通常
用いられているが、コスト高となつていた。
この銀電極のコスト高を改消するため、近年セ
ラミツクコンデンサにおいてはメツキ電極の有効
性が認められ、銀電極に代る低コスト電極として
実用化されている。
しかしながら、Bi、Cu、Pb、Ｂなどの粒界絶
縁化剤を拡散し、磁器の粒界を絶縁化してなる粒
界絶縁型半導体磁器に無電解メツキ電極を施し、
得られた半導体コンデンサを高温負荷試験したと
ころ絶縁抵抗の劣化が著しく、半導体コンデンサ
の無電解メツキ電極化への実用化の大きな障害と
なつていた。
本発明は上記の欠点を改良するもので、
SrTiO3を主成分とする半導体磁器にBi、Cu、
Pb、Ｂなどの粒界絶縁化剤と、該粒界絶縁化剤
に１〜200重量％のガラスフリツトを混合してな
る拡散剤を塗布して拡散させたのち、無電解メツ
キ電極を付与することにより得られた粒界絶縁型
半導体コンデンサは、高温負荷での絶縁抵抗劣化
現象が著しく改善されることを見い出したもの
で、第１図に高温負荷試験結果を示す。○イは銀電
極を有する粒界絶縁型半導体コンデンサ。○ロは本
発明のメツキ電極を有する粒界絶縁型半導体コン
デンサ。○ハ従来のメツキ電極を有する粒界絶縁型
半導体コンデンサを示し、この第１図からわかる
ように本発明品は従来の銀電極を有する粒界絶縁
型半導体コンデンサと同等の電気特性および信頼
性をもち、かつ従来の銀電極品に比較して極めて
安価であり、また従来のメツキ電極品の欠点を解
消したものである。
以下、本発明を実施例に基き詳細に説明する。
SrTiO3を主成分とする円板形の半導体磁器
（磁器寸法12.5mmφ、厚み0.45mm）に第１表のよ
うにBi、Cu、Pb、Ｂのうち１種または２種以上
からなる粒界絶縁化剤と、該粒界絶縁化剤に対し
て１〜200重量％のホウケイ酸鉛ガラスを混合し、
さらにバインダーを加えてペースト状にした拡散
剤を半導体磁器表面に塗布し、温度1150〜1200℃
で２時間粒界拡散を行ない粒界絶縁化半導体磁器
を得た。次いで該粒界絶縁化半導体磁器の表面に
通常の無電解メツキ法によりニツケルメツキを施
し、その後外周研磨して11.6mmφとし、ニツケル
メツキ電極を形成した。このように電極が施され
た粒界絶縁型半導体磁器に引出リードを半田接続
し外装して完成する。
このようにして得られた粒界絶縁型半導体コン
デンサについて、容量、誘電体損失、絶縁抵抗お
よび破壊電圧を測定すると共に高温負荷試験を行
ない、1000時間後の絶縁抵抗について測定した。
その結果を第１表に示す。
The present invention utilizes strontium titanate (hereinafter referred to as strontium titanate).
It is an improved electrode of a grain boundary insulated semiconductor capacitor whose main component is SrTiO 3 ), and has electrical characteristics and reliability comparable to or comparable to those of conventional grain boundary insulated semiconductor capacitors with silver electrodes. The present invention also provides a method for manufacturing a grain boundary insulated semiconductor capacitor having an inexpensive plated electrode. Grain boundary insulated semiconductor capacitors whose main component is SrTiO 3 have excellent temperature characteristics, DC bias, etc.
In addition, since it has an extremely high dielectric constant, it is often used in low-voltage electronic circuits as an excellent semiconductor capacitor with a small size and large capacity. However, as with conventional ceramic capacitors and reoxidation type semiconductor capacitors, electrodes containing silver as a main component are usually used for the electrodes of this grain boundary insulated semiconductor capacitor, but these are expensive. In order to reduce the high cost of silver electrodes, plating electrodes have recently been recognized as effective in ceramic capacitors, and have been put into practical use as low-cost electrodes in place of silver electrodes. However, when grain boundary insulated semiconductor porcelain is made by diffusing grain boundary insulating agents such as Bi, Cu, Pb, and B to insulate the grain boundaries of the porcelain, electroless plating electrodes are applied.
When the obtained semiconductor capacitor was subjected to a high temperature load test, the insulation resistance deteriorated significantly, which was a major obstacle to the practical application of electroless plating electrodes of semiconductor capacitors. The present invention aims to improve the above-mentioned drawbacks.
Bi , Cu,
Applying and diffusing a grain boundary insulating agent such as Pb or B and a diffusing agent made by mixing 1 to 200% by weight of glass frit with the grain boundary insulating agent, and then applying an electroless plating electrode. It has been found that the grain boundary insulated semiconductor capacitor obtained by the method has a marked improvement in the insulation resistance deterioration phenomenon under high temperature load, and the high temperature load test results are shown in FIG. ○A is a grain boundary insulated semiconductor capacitor with silver electrodes. ○B is a grain boundary insulated semiconductor capacitor having a plating electrode of the present invention. ○C shows a conventional grain boundary insulated semiconductor capacitor with plating electrodes. As can be seen from Figure 1, the product of the present invention has the same electrical characteristics and reliability as the conventional grain boundary insulated semiconductor capacitors with silver electrodes. It is durable and extremely inexpensive compared to conventional silver electrode products, and also eliminates the drawbacks of conventional plating electrode products. Hereinafter, the present invention will be explained in detail based on examples. As shown in Table 1, grain boundary insulation consisting of one or more of Bi, Cu, Pb, and B is applied to a disk-shaped semiconductor porcelain (porcelain size: 12.5 mmφ, thickness: 0.45 mm) whose main component is SrTiO 3 . mixing agent and lead borosilicate glass in an amount of 1 to 200% by weight based on the grain boundary insulating agent,
Furthermore, a binder is added to make a paste-like diffusing agent, which is then applied to the surface of the semiconductor porcelain at a temperature of 1150 to 1200℃.
Grain boundary diffusion was carried out for 2 hours to obtain grain boundary insulated semiconductor porcelain. Next, the surface of the grain boundary insulated semiconductor ceramic was nickel plated by a conventional electroless plating method, and then the outer periphery was polished to a diameter of 11.6 mm to form a nickel plated electrode. The grain-boundary insulated semiconductor porcelain provided with the electrodes is connected with lead leads by soldering and packaged to complete the process. Regarding the grain boundary insulated semiconductor capacitor thus obtained, the capacitance, dielectric loss, insulation resistance, and breakdown voltage were measured, and a high temperature load test was also conducted, and the insulation resistance after 1000 hours was measured.
The results are shown in Table 1.
【表】
なお、第１表中No.15は比較のための銀電極を有
する粒界絶縁型半導体コンデンサ、No.１、２、
７、８、14は本発明の範囲外である。また容量、
誘電体損失については測定電圧1Vrms、周波数
1KHz、温度25℃で測定し、高温負荷試験は温度
85±２℃の槽中で37.5VDCを印加し、1000時間
後の絶縁抵抗値である。第１表で明らかなように
本発明の無電解メツキ電極品はBi―Cu―Pb―Ｂ
などの拡散剤のみによる従来の粒界絶縁型半導体
磁器に無電解メツキ電極を設けたものに比較して
電気的特性が安定し、高温負荷試験における絶縁
抵抗も極めて安定である。
このようにSrTiO3を主体とする半導体磁器に
Bi―CuあるいはBi―Cu―Pb―Ｂなどの粒界絶縁
化剤と、該絶縁化剤に対して1.0〜200重量％のガ
ラス粉末を混合した拡散剤を塗布して粒界に拡散
し粒界絶縁化したのち、無電解メツキ法によりメ
ツキ電極を施こした本発明の粒界絶縁型半導体コ
ンデンサで、従来の銀電極品と同等の諸特性を有
し、かつ信頼性に優れ安価なものである。
なお、上記実施例でメツキ電極を無電極ニツケ
ルメツキによる電極形成法について説明したが、
例えば銅メツキ電極などについても同様の効果を
有する。また粒界絶縁化剤をBi―CuとBi―Cu―
Pb―Ｂについて説明したが、Bi、Cu、Pb、Ｂの
１種でもよく、２種以上を組合せ混合するとなお
よく、このほかＷ、Ta、Th、Co、Ni、Mnなど
の金属酸化物においても同様の効果が得られる。
さらにこれらの粒界絶縁化剤に混合するガラス粉
末はホウケイ酸鉛ガラスに限らず、Ｂ―Si―Pb、
Zn―Si―Ｂ、Ba―Si―Ｂなど軟化度を、300〜
900℃の範囲にもつガラス組成系のものが最適で
ある。
以上のように本発明はSrTiO3を主成分とする
半導体磁器の粒界を絶縁化する粒界絶縁化剤にガ
ラス粉末を混合した拡散剤として塗布などし拡散
して粒界を絶縁化しているので、電極形成に際し
て無電解メツキを施こし、安価に電極形成ができ
ると共に信頼性に優れ、工業上有益なものであ
る。[Table] In Table 1, No. 15 is a grain boundary insulated semiconductor capacitor with a silver electrode for comparison, Nos. 1, 2,
7, 8, and 14 are outside the scope of the present invention. Also capacity,
For dielectric loss, measurement voltage 1Vrms, frequency
Measured at 1KHz, temperature 25℃, high temperature load test
This is the insulation resistance value after 1000 hours when 37.5VDC was applied in a bath at 85±2°C. As is clear from Table 1, the electroless plating electrode product of the present invention has Bi-Cu-Pb-B
Compared to conventional grain-boundary insulated semiconductor porcelain with electroless plating electrodes using only a diffusing agent, the electrical properties are more stable, and the insulation resistance in high-temperature load tests is also extremely stable. In this way, semiconductor porcelain mainly composed of SrTiO 3
A dispersing agent made by mixing a grain boundary insulating agent such as Bi-Cu or Bi-Cu-Pb-B with glass powder of 1.0 to 200% by weight relative to the insulating agent is applied and diffused into the grain boundaries. The grain boundary insulated semiconductor capacitor of the present invention is made of a grain boundary insulated semiconductor capacitor in which a plating electrode is applied by an electroless plating method after interlayer insulation, and the capacitor has properties equivalent to conventional silver electrode products, and is highly reliable and inexpensive. It is. In addition, in the above example, the method of forming the plated electrode by electrodeless nickel plating was explained.
For example, copper plating electrodes have similar effects. In addition, grain boundary insulating agents are Bi-Cu and Bi-Cu-
Although Pb-B has been explained, it may be used alone of Bi, Cu, Pb, and B, and it is even better to mix two or more of them.In addition, metal oxides such as W, Ta, Th, Co, Ni, and Mn A similar effect can be obtained.
Furthermore, the glass powder mixed with these grain boundary insulating agents is not limited to lead borosilicate glass, but also B-Si-Pb,
Softening degree such as Zn-Si-B, Ba-Si-B, etc. from 300 to
Glass compositions that can withstand temperatures in the 900°C range are optimal. As described above, the present invention insulates the grain boundaries of semiconductor porcelain whose main component is SrTiO 3 by coating and diffusing glass powder as a diffusion agent in a grain boundary insulating agent that insulates the grain boundaries of semiconductor ceramics. Therefore, when forming electrodes, electroless plating is performed, and the electrodes can be formed at low cost and have excellent reliability, which is industrially useful.
第１図は高温負荷試験による絶縁抵抗−時間特
性図である。
FIG. 1 is an insulation resistance-time characteristic diagram obtained from a high-temperature load test.
Claims (1)
体磁器の粒界を絶縁化するビスマス、銅、鉛、ホ
ウ素などよりなる粒界絶縁化剤と該粒界絶縁化剤
に対して１〜200重量％のガラス粉末とを添加混
合してなる拡散剤を半導体磁器に塗布し、拡散し
て粒界を絶縁化したのち、無電解メツキを施して
メツキ電極を形成したことを特徴とする粒界絶縁
型半導体コンデンサの製造方法。1. A grain boundary insulating agent made of bismuth, copper, lead, boron, etc. that insulates the grain boundaries of semiconductor porcelain mainly composed of strontium titanate, and 1 to 200% by weight of glass based on the grain boundary insulating agent. A grain boundary insulated semiconductor capacitor characterized in that a diffusing agent made by adding and mixing a powder is applied to semiconductor porcelain, diffused to insulate the grain boundaries, and then subjected to electroless plating to form a plating electrode. manufacturing method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10466180A JPS5730310A (en) | 1980-07-29 | 1980-07-29 | Grain boundary insulation type semiconductor condenser |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10466180A JPS5730310A (en) | 1980-07-29 | 1980-07-29 | Grain boundary insulation type semiconductor condenser |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5730310A JPS5730310A (en) | 1982-02-18 |
| JPH0154848B2 true JPH0154848B2 (en) | 1989-11-21 |
Family
ID=14386642
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10466180A Granted JPS5730310A (en) | 1980-07-29 | 1980-07-29 | Grain boundary insulation type semiconductor condenser |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5730310A (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6119877A (en) * | 1986-12-18 | 2000-09-19 | G & G Intellectual Properties, Inc. | Adjustable vehicle-carrying frame |
| US5417332A (en) * | 1986-12-18 | 1995-05-23 | G & G Intellectual Properties, Inc. | Adjustable vehicle-carrying frame |
| JPH02133908A (en) * | 1988-11-15 | 1990-05-23 | Tdk Corp | Surface-layer type semiconductor ceramic capacitor and its manufacture |
| US5415505A (en) * | 1991-10-30 | 1995-05-16 | G & G Intellectual Properties, Inc. | Vehicle-carrying frame |
| US5769591A (en) * | 1993-02-04 | 1998-06-23 | Kar-Tainer International, Inc. | Frame structure and method of packing vehicle bodies |
| US5454672A (en) * | 1993-03-17 | 1995-10-03 | G & G Intellectual Properties, Inc. | Adjustable load-carrying frame for fully utilizing transport enclosure space |
| US5924248A (en) * | 1995-08-02 | 1999-07-20 | Kar-Tainer International Inc. | Collapsible frame device |
-
1980
- 1980-07-29 JP JP10466180A patent/JPS5730310A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5730310A (en) | 1982-02-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR920003225B1 (en) | Semiconductive ceramic composition | |
| KR100366928B1 (en) | Conductive paste and ceramic electronic component | |
| JPS63927B2 (en) | ||
| US3760244A (en) | Ceramic capacitor and method of forming same | |
| JPH0154848B2 (en) | ||
| JPH0226775B2 (en) | ||
| JP3419321B2 (en) | Ceramic electronic component and method of manufacturing the same | |
| JPH09190950A (en) | Outer electrode of electronic part | |
| JPH11106259A (en) | Dielectric ceramic composition | |
| JPH04293214A (en) | Conductive paste for chip type electronic component | |
| JPS6127003A (en) | Conductive paste composition | |
| US4709299A (en) | Low temperature sintered ceramic capacitor with a temperature compensating capability, and method of manufacture | |
| JP3123310B2 (en) | Conductive paste for chip-type electronic components | |
| JPH0154849B2 (en) | ||
| JP3656860B2 (en) | Non-reducing dielectric ceramic composition | |
| JPH0636970A (en) | External electrode of chip type electronic component | |
| US4769354A (en) | Type I dielectric composition based on neodymium titanate | |
| JPS6133251B2 (en) | ||
| JP2693249B2 (en) | Low loss porcelain capacitor | |
| JPH0734415B2 (en) | Grain boundary insulation type semiconductor porcelain composition | |
| JPH02150007A (en) | Laminated porcelain capacitor | |
| JPS59127826A (en) | Grain boundary insulating semiconductor porcelain capacitor | |
| KR920009172B1 (en) | Semiconductive ceramic composition and semiconductive ceramic capacitor | |
| JPH038759A (en) | Semiconductive porcelain material | |
| JPH0674166B2 (en) | Porcelain composition for low temperature firing |