JPH02111006A - Manufacture of grain-boundary insulated semiconductor porcelain capacitor - Google Patents
Manufacture of grain-boundary insulated semiconductor porcelain capacitorInfo
- Publication number
- JPH02111006A JPH02111006A JP26472088A JP26472088A JPH02111006A JP H02111006 A JPH02111006 A JP H02111006A JP 26472088 A JP26472088 A JP 26472088A JP 26472088 A JP26472088 A JP 26472088A JP H02111006 A JPH02111006 A JP H02111006A
- Authority
- JP
- Japan
- Prior art keywords
- grain
- semiconductor porcelain
- insulated
- agent
- grain boundary
- 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
- 239000004065 semiconductor Substances 0.000 title claims abstract description 46
- 229910052573 porcelain Inorganic materials 0.000 title claims abstract description 25
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- 239000003990 capacitor Substances 0.000 title abstract description 5
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000011521 glass Substances 0.000 claims abstract description 15
- 239000000843 powder Substances 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 239000003985 ceramic capacitor Substances 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 4
- 238000009792 diffusion process Methods 0.000 abstract description 9
- 238000010438 heat treatment Methods 0.000 abstract description 5
- 238000009826 distribution Methods 0.000 abstract description 3
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- 239000000919 ceramic Substances 0.000 description 6
- 238000007747 plating Methods 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 238000005452 bending Methods 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- 238000007772 electroless plating Methods 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 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
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、電極としてメッキ電極を用いる粒界絶縁型半
導体磁器コンデンサの製造方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method of manufacturing a grain boundary insulated semiconductor ceramic capacitor using a plated electrode as an electrode.
（従来技術）
従来、この種の粒界絶縁型半導体磁器コンデンサの製造
方法には、特開昭５７−３０３１０号公報に記載された
ものがある。(Prior Art) A conventional method for manufacturing this type of grain boundary insulated semiconductor ceramic capacitor is described in Japanese Patent Laid-Open No. 57-30310.
この粒界絶縁型磁器コンデンサの製造方法は、粒界絶縁
型半導体磁器コンデンサの電極としてこれまで用いてき
た銀電極に代わる低コストのメッキ電極を用いるために
案出されたものである。This method of manufacturing a grain boundary insulated ceramic capacitor was devised to use a low-cost plated electrode in place of the silver electrode that has been used hitherto as an electrode for a grain boundary insulated semiconductor ceramic capacitor.
具体的には、チタン酸ストロンチウムを主体とする半導
体磁器に、ビスマス、銅、鉛、ホウ素などからなる粒界
絶縁化剤とガラス粉末とを混合してなる拡散剤を塗布し
、熱拡散して粒界を絶縁化したのち、両主表面に無電解
メッキによってメッキ電極を形成するものである。Specifically, a diffusing agent made by mixing a grain boundary insulating agent made of bismuth, copper, lead, boron, etc. and glass powder is applied to semiconductor porcelain mainly made of strontium titanate, and then thermally diffused. After insulating the grain boundaries, plating electrodes are formed on both main surfaces by electroless plating.
（従来技術の問題点）
しかしながら、上述した粒界絶縁型半導体磁器コンデン
サの製造方法では、粒界絶縁化剤とガラス粉末とを混合
した拡散剤を塗布する工程があるために、工程数が増え
、コストも増加した。(Problems with the prior art) However, in the method for manufacturing the grain boundary insulated semiconductor ceramic capacitor described above, the number of steps increases because there is a step of applying a diffusion agent that is a mixture of a grain boundary insulating agent and glass powder. , costs also increased.
また、拡散剤の塗布量や熱処理時の熱分布のバラツキに
よって生じる拡散剤の拡散エネルギーのバラツキ、ある
いは拡散剤が塗布された部分とされない部分があること
によるガラス粉末の拡散度合の変化によって、コンデン
サの容量にバラツキが生じ特性が劣化することがあった
。In addition, variations in the diffusion energy of the diffusing agent caused by variations in the amount of the diffusing agent applied or the heat distribution during heat treatment, or changes in the degree of diffusion of the glass powder due to the fact that some parts are coated with the diffusing agent and others are not, can cause damage to the capacitor. There were cases where variations occurred in the capacity and the characteristics deteriorated.
さらに、拡散エネルギーのバラツキによって、粒子間に
拡散剤が不均一に介在するため、結合強度にもバラツキ
が生じ抗折強度が弱く、メッキ工程でワレやカケなどの
不良が生じることがあった。Furthermore, due to variations in diffusion energy, the diffusing agent is unevenly interposed between particles, resulting in variations in bonding strength, resulting in weak bending strength, which may result in defects such as cracking and chipping during the plating process.
そこで本発明は、上述した問題点を解決しようとしたも
のであり、粒界絶縁型半導体磁器コンデンサの電極とし
てメッキ電極を用いても銀電惰と同等の電気特性、信頼
性をもち、しかも高抗折強度でメッキ工程でのワレ、カ
ケを減少することができる粒界絶縁型半導体磁器コンデ
ンサの製造方法を提供することを目的とするものである
。Therefore, the present invention is an attempt to solve the above-mentioned problems, and even if plated electrodes are used as the electrodes of grain boundary insulated semiconductor ceramic capacitors, they have the same electrical characteristics and reliability as silver electrodes, and have high performance. It is an object of the present invention to provide a method for manufacturing a grain boundary insulated semiconductor ceramic capacitor that can reduce cracking and chipping during the plating process due to its bending strength.
（問題点を解決するための手段）
本発明の粒界絶縁型半導体磁器コンデンサの製造方法は
、
半導体磁器を準備する工程と、
この半導体磁器と、この半導体磁器の粒界を絶縁化する
粒界絶縁化剤およびこの粒界絶縁化剤に対して１重量５
ｃ〜１００重量％のガラス粉末を添加してなる拡散剤と
を混合して撹拌しながら熱処理し半導体磁器の粒界を絶
縁化する工程と、粒界が絶縁化された半導体磁器の両主
表面にメッキ電極を形成する工程、
とからなる。(Means for Solving the Problems) The method for manufacturing a grain boundary insulated semiconductor ceramic capacitor of the present invention includes a step of preparing semiconductor ceramic, and a grain boundary for insulating the grain boundaries of the semiconductor ceramic and the semiconductor ceramic. 1 weight 5 for the insulating agent and this grain boundary insulating agent
c - A process of insulating the grain boundaries of the semiconductor porcelain by mixing with a diffusing agent made by adding 100% by weight of glass powder and heat-treating the mixture while stirring, and both main surfaces of the semiconductor porcelain with the grain boundaries insulated. A process of forming a plating electrode on the plated electrode.
（作用）
本発明の粒界絶縁型半導体磁器コンデンサの製造方法に
よれば、半導体磁器と、粒界絶縁化剤およびガラス粉末
とからなる拡散剤とを混合して撹拌しながら熱処理し半
導体磁器の粒界をを絶縁化するので、拡散剤の塗布量や
熱処理時の熱分布が均一となり、拡散エネルギーのバラ
ツキがなくなる。(Function) According to the method for manufacturing a grain boundary insulated semiconductor ceramic capacitor of the present invention, semiconductor ceramics and a diffusing agent consisting of a grain boundary insulating agent and glass powder are mixed and heat-treated while stirring. Since the grain boundaries are insulated, the amount of diffusion agent applied and the heat distribution during heat treatment are uniform, and variations in diffusion energy are eliminated.
また、拡散剤が塗布されない部分がなくなるので、ガラ
ス粉末の拡散度合が変化することがなくなる。Furthermore, since there are no areas to which the diffusing agent is applied, the degree of diffusion of the glass powder does not change.
（実施例）
以下に、本発明の粒界絶縁型半導体磁器コンデンサの製
造方法を詳細に説明する。(Example) Below, a method for manufacturing a grain boundary insulated semiconductor ceramic capacitor of the present invention will be described in detail.
まず、５ｒＴｉＯ３（９９、０ｍｏ１％）とＹ２Ｏ３（
１、Ｏｍ。First, 5rTiO3 (99, 0mo1%) and Y2O3 (
1. Om.
）％）からなる混合物を１１５０℃で２時間仮焼したの
ち、バインダーを加えて造粒し、直径１．０ｍｍ厚みＱ
、４ｍｍの円板状に成形した。そして、この円板状に成
形した成形物を１１００℃で２時間予備焼成を行ない、
さらにＮ−１１からなる還元雰囲気中において１４３０
℃で３時間焼成し、半導体磁器を得た。)%) was calcined at 1150°C for 2 hours, a binder was added and the mixture was granulated to give a diameter of 1.0 mm and a thickness of Q.
, and was molded into a 4 mm disk shape. Then, this disc-shaped molded product was pre-fired at 1100°C for 2 hours,
Furthermore, in a reducing atmosphere consisting of N-11, 1430
It was fired at ℃ for 3 hours to obtain semiconductor porcelain.
次に、Ｂｉ−Ｐｂ−Ｃｕ−Ｂ系のガラス粉末とＢｉ２０
３−ＰｂＯ−ＣｕＯとを第１表に示す割合で混合した混
合物である拡散剤を、上記半導体磁器の１．５重量％に
なるように秤量した。Next, Bi-Pb-Cu-B glass powder and Bi20
A diffusing agent, which is a mixture of 3-PbO-CuO and 3-PbO-CuO in the proportions shown in Table 1, was weighed so as to account for 1.5% by weight of the semiconductor ceramic.
次に、この拡散剤を上記半導体磁器１０００個とともに
円筒形の匣の中へ入れ、この匣が炉内で回転することに
よって匣内で半導体磁器と拡散剤を混合して撹拌しなが
ら、酸化雰囲気中、１１２０℃で１時間熱処理を行ない
、半導体磁器の粒界を絶縁化した。Next, this diffusing agent is placed in a cylindrical box together with 1000 pieces of the semiconductor porcelain, and as this box rotates in the furnace, the semiconductor porcelain and the diffusing agent are mixed and stirred in the box, and an oxidizing atmosphere is created. Heat treatment was performed at 1120° C. for 1 hour to insulate the grain boundaries of the semiconductor ceramic.
次に、熱処理後の半導体磁器の端面にメッキレジストを
塗布した後、無電解メッキによって半導体磁器の両主表
面にニッケルメッキ電極を形成し、粒界絶縁型半導体磁
雅コンデンサを得た。Next, a plating resist was applied to the end face of the heat-treated semiconductor porcelain, and then nickel-plated electrodes were formed on both main surfaces of the semiconductor porcelain by electroless plating to obtain a grain boundary insulated semiconductor magnetic capacitor.
このようにして得られた粒界絶縁型半導体磁器コンデン
サについて、静電容量（ｎＦ）、標準偏差昏尋、溶着率
（％）、抗折強度（ｋｇ）ワレ・カケ不良率（％）！
および誘電損失（％）を測定し、この結果を第１表に示
した。Regarding the grain boundary insulated semiconductor ceramic capacitor thus obtained, the capacitance (nF), standard deviation, welding rate (%), bending strength (kg), crack/chip defect rate (%)! and dielectric loss (%) were measured, and the results are shown in Table 1.
方法によって作製された粒界絶縁型半導体磁器コンデン
サである。This is a grain boundary insulated semiconductor ceramic capacitor fabricated by this method.
また、第１表中において粒界絶縁化剤Ａは１３ ｉ ２
０３−ＰｂＯ−ＣｕＯの組成で重量比が４０：４０：２
０であり、粒界絶縁化剤ＢはＢ ｉ ２０３−ＰｂＯ−
ＣｕＯの組成で重量比が９０：２：８である。In addition, in Table 1, grain boundary insulating agent A is 13 i 2
03-PbO-CuO composition with a weight ratio of 40:40:2
0, and the grain boundary insulating agent B is B i 203-PbO-
The CuO composition has a weight ratio of 90:2:8.
さらに、第１表中においてガラス粉末ＣはＢｉ２０３−
ＰｂＯ−ＣｕＯ−Ｂ２０３の組成で重量比が３０：３０
：１０：３０であり、ガラス粉末りは旧２０３−ＰｂＯ
−ＣｕＯ−Ｂ２０３の組成で重量比が２５：２０：２５
：３０である。Furthermore, in Table 1, glass powder C is Bi203-
PbO-CuO-B203 composition with a weight ratio of 30:30
:10:30, and the glass powder was old 203-PbO.
-CuO-B203 composition with a weight ratio of 25:20:25
:30.
この第１表から明らかなように、試料Ｎｏ、 ｌ 。As is clear from this Table 1, sample No. 1.
７のようにガラス粉末の添加量が粒界絶縁化剤に対して
１重量％より小さい場合、試１１１１Ｎｏ、５．１１の
ようにガラス粉末の添加量が粒界絶縁化剤に対して１０
０重量％より大きい場合、または試料Ｎｏ。When the amount of glass powder added is less than 1% by weight relative to the grain boundary insulating agent as in 7, the amount of glass powder added is less than 1% by weight relative to the grain boundary insulating agent as in Trial 1111No.5.11.
If it is greater than 0% by weight, or sample no.
６のように従来の製造方法で作製した場合のいずれの場
合と比較しても、静電容量のバラツキが小さく、抗折強
度も大きい。また、ワレ、カケ不良率が低いので良品率
が高くなる。Compared to any of the cases manufactured using conventional manufacturing methods such as No. 6, the variation in capacitance is small and the bending strength is also large. In addition, since the defective rate of cracks and chips is low, the rate of non-defective products is high.
なお、本発明の説明において、無電解メッキによってニ
ッケルメッキ電極を形成したものを示したが、ニッケル
メッキ電極に限るものではなく、銅メッキ電極等でもよ
い。In the description of the present invention, a nickel plated electrode formed by electroless plating is shown, but the present invention is not limited to a nickel plated electrode, and a copper plated electrode or the like may be used.
さらに、半導体磁器と拡散剤を混合して撹拌しながら熱
処理を行う際、匣の中に半導体磁器と拡散剤を入れ、回
転させながら熱処理を行う方法を示したが、これに限る
ものではなく、匣を前後あるいは左右に移動させながら
熱処理を行う方法でもよい。Furthermore, when heat-treating a mixture of semiconductor porcelain and a diffusing agent while stirring, we have shown a method in which the semiconductor porcelain and diffusing agent are placed in a box and heat-treated while being rotated, but the method is not limited to this. The heat treatment may be performed while moving the box back and forth or left and right.
（発明の効果）
以上のように、本発明の粒界絶縁型半導体磁器コンデン
サの製造方法を用いれば、拡散剤の拡散エネルギーが均
一となり、安定に粒界を絶縁化することができる。また
、このことによってコンデンサの静電容量のバラツキあ
るいはワレ、カケ等の不良率を小さくすることができる
ので、粒界絶縁型半導体磁器コンデンサの信頼性を向上
することができる。(Effects of the Invention) As described above, by using the method for manufacturing a grain boundary insulated semiconductor ceramic capacitor of the present invention, the diffusion energy of the diffusing agent becomes uniform, and grain boundaries can be stably insulated. Furthermore, this makes it possible to reduce variations in the capacitance of the capacitor or the defect rate such as cracks and chips, thereby improving the reliability of the grain boundary insulated semiconductor ceramic capacitor.
Claims (1)
粒界絶縁化剤およびこの粒界絶縁化剤に対して１重量％
〜１００重量％のガラス粉末を添加してなる拡散剤とを
混合して撹拌しながら熱処理し半導体磁器の粒界を絶縁
化する工程と、 粒界が絶縁化された半導体磁器の両主表面にメッキ電極
を形成する工程、 とからなる粒界絶縁型半導体磁器コンデンサの製造方法
。[Claims] A step of preparing semiconductor porcelain, the semiconductor porcelain, a grain boundary insulating agent for insulating the grain boundaries of the semiconductor porcelain, and 1% by weight of the grain boundary insulating agent.
A process of insulating the grain boundaries of the semiconductor porcelain by mixing with a diffusing agent made by adding ~100% by weight of glass powder and heat-treating the mixture while stirring, and a process of insulating the grain boundaries of the semiconductor porcelain on both main surfaces of the semiconductor porcelain whose grain boundaries have been insulated. A method for manufacturing a grain boundary insulated semiconductor ceramic capacitor, comprising: forming a plated electrode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26472088A JPH0648665B2 (en) | 1988-10-20 | 1988-10-20 | Method for manufacturing grain boundary insulated semiconductor ceramic capacitor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26472088A JPH0648665B2 (en) | 1988-10-20 | 1988-10-20 | Method for manufacturing grain boundary insulated semiconductor ceramic capacitor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02111006A true JPH02111006A (en) | 1990-04-24 |
| JPH0648665B2 JPH0648665B2 (en) | 1994-06-22 |
Family
ID=17407246
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26472088A Expired - Fee Related JPH0648665B2 (en) | 1988-10-20 | 1988-10-20 | Method for manufacturing grain boundary insulated semiconductor ceramic capacitor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0648665B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2492933A2 (en) | 2011-02-24 | 2012-08-29 | Murata Manufacturing Co., Ltd. | Grain Boundary-Insulated Semiconductor Ceramic, Semiconductor Ceramic Capacitor, and Method for Producing Semiconductor Ceramic Capacitor |
-
1988
- 1988-10-20 JP JP26472088A patent/JPH0648665B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2492933A2 (en) | 2011-02-24 | 2012-08-29 | Murata Manufacturing Co., Ltd. | Grain Boundary-Insulated Semiconductor Ceramic, Semiconductor Ceramic Capacitor, and Method for Producing Semiconductor Ceramic Capacitor |
| JP2012171852A (en) * | 2011-02-24 | 2012-09-10 | Murata Mfg Co Ltd | Grain boundary-insulated semiconductor ceramic, semiconductor ceramic capacitor, and method for producing the semiconductor ceramic capacitor |
| US8476179B2 (en) | 2011-02-24 | 2013-07-02 | Murata Manufacturing Co., Ltd. | Grain boundary-insulated semiconductor ceramic, semiconductor ceramic capacitor, and method for producing semiconductor ceramic capacitor |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0648665B2 (en) | 1994-06-22 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |