JP2003243246A - Laminated ceramic electronic component - Google Patents
Laminated ceramic electronic componentInfo
- Publication number
- JP2003243246A JP2003243246A JP2002037956A JP2002037956A JP2003243246A JP 2003243246 A JP2003243246 A JP 2003243246A JP 2002037956 A JP2002037956 A JP 2002037956A JP 2002037956 A JP2002037956 A JP 2002037956A JP 2003243246 A JP2003243246 A JP 2003243246A
- Authority
- JP
- Japan
- Prior art keywords
- electronic component
- external electrode
- ceramic
- ceramic electronic
- internal conductor
- 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
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、内部電極（内部導
体）と外部電極との接続性が改善されて、歩留りの好適
な、積層セラミックコンデンサ等の積層セラミック電子
部品に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a monolithic ceramic electronic component such as a monolithic ceramic capacitor in which the connectivity between internal electrodes (internal conductors) and external electrodes is improved and the yield is favorable.
【０００２】[0002]
【従来の技術】従来のセラミック電子部品、例えば積層
セラミック電子部品は、セラミック素体と、セラミック
素体内部のセラミック層間に形成された内部電極と、セ
ラミック素体の両端面に形成された外部電極とを有して
いる。2. Description of the Related Art A conventional ceramic electronic component, for example, a multilayer ceramic electronic component, includes a ceramic body, internal electrodes formed between ceramic layers inside the ceramic body, and external electrodes formed on both end surfaces of the ceramic body. And have.
【０００３】セラミック素体は複数のセラミック層が積
層されてなっている。内部電極を備える積層セラミック
電子部品にあっては、内部電極のそれぞれの端縁がセラ
ミック層の何れかの端面に露出するようにセラミック層
間に形成され、外部電極は内部電極の露出した端縁を介
して内部電極と電気的に接続されている。The ceramic body is formed by laminating a plurality of ceramic layers. In a monolithic ceramic electronic component including internal electrodes, the internal electrodes are formed between the ceramic layers so that each edge is exposed on either end surface of the ceramic layer, and the external electrodes are formed by exposing the exposed edges of the internal electrodes. It is electrically connected to the internal electrode via.
【０００４】厚膜からなる外部電極の場合、導電性ペー
ストが用いられる。この導電性ペーストは、例えば銀
（Ａｇ）、Ａｇ−パラジウム（Ｐｄ）合金、銅（Ｃ
ｕ）、ニッケル（Ｎｉ）などからなる導電性粉末とガラ
スフリットとが有機バインダーと有機溶剤とからなる有
機ビヒクル中に分散されてなり、セラミック素体の端面
に浸漬塗布して乾燥させ焼成されることにより外部電極
を形成できるものである。In the case of a thick film external electrode, a conductive paste is used. This conductive paste is, for example, silver (Ag), Ag-palladium (Pd) alloy, copper (C).
u), a conductive powder made of nickel (Ni), etc. and a glass frit are dispersed in an organic vehicle made of an organic binder and an organic solvent. The ceramic body is dip coated, dried and fired. Thus, the external electrode can be formed.
【０００５】さらに、外部電極のはんだ濡れ性やはんだ
耐熱性を向上させる目的で、導電性ペーストからなる外
部電極上にＮｉめっきを、さらにその上にＳｎめっき或
いははんだめっきなどの各種電解めっきを施す場合があ
る。Further, for the purpose of improving the solder wettability and the solder heat resistance of the external electrode, the external electrode made of a conductive paste is plated with Ni, and then various electrolytic plating such as Sn plating or solder plating is performed thereon. There are cases.
【０００６】近年、積層セラミック電子部品としての、
例えば積層セラミックコンデンサにおいてはコストダウ
ンに対応するため、内部電極材料に卑金属、特にＮｉを
主成分とする金属を使用する場合が多い。Ｎｉを主成分
とする内部電極の採用に対応し、外部電極も非酸化性雰
囲気での焼成により形成する必要があり、Ｎｉと合金を
形成し易い卑金属であるＣｕを用いることが多い。Recently, as a monolithic ceramic electronic component,
For example, in a multilayer ceramic capacitor, a base metal, particularly a metal containing Ni as a main component is often used as an internal electrode material in order to reduce cost. Corresponding to the adoption of the internal electrode containing Ni as a main component, the external electrode also needs to be formed by firing in a non-oxidizing atmosphere, and Cu, which is a base metal that easily forms an alloy with Ni, is often used.
【０００７】[0007]
【発明が解決しようとする課題】内部電極の主成分がＮ
ｉの場合、外部電極の導電成分にはＣｕを用いることが
多い。これは外部電極焼成時、内部電極Ｎｉと外部電極
Ｃｕの金属間で固相相互拡散が起こることによって、Ｎ
ｉ−Ｃｕ合金が形成され、両者間に強固な接合が確保さ
れるためである。DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention
In the case of i, Cu is often used as the conductive component of the external electrode. This is because solid phase interdiffusion occurs between the metals of the internal electrode Ni and the external electrode Cu during firing of the external electrode.
This is because an i-Cu alloy is formed and a strong bond is secured between the two.
【０００８】ところで、外部電極中には、外部電極と素
子との接合性向上やめっき液の浸入防止などを目的と
し、ガラスフリットが含まれる。ガラスフリットとし
て、従来から、ホウ酸系ガラスやホウケイ酸系ガラス、
アルミン酸系ガラスが用いられることが多い。ガラスフ
リットには、修飾元素として亜鉛酸化物やアルカリ土類
金属酸化物などが用いられている。By the way, the external electrode contains a glass frit for the purpose of improving the bondability between the external electrode and the element and preventing the penetration of the plating solution. As a glass frit, conventionally, boric acid glass or borosilicate glass,
Aluminate glass is often used. Zinc oxide, alkaline earth metal oxide, or the like is used as a modifying element in the glass frit.
【０００９】外部電極の焼成時、ガラスは軟化し外部電
極／内部電極界面に流動する。この液相となったガラス
中へ内部電極構成成分であるＮｉが溶解・拡散し、さら
に外部電極Ｃｕ上へ析出し内部へと拡散する。このた
め、内部電極先端部が消失し、内部電極が見掛け上内部
に引っ込んだ構造になる。これにより、内部電極と外部
電極との電気的な接続が十分に得られず、積層セラミッ
ク電子部品の電気的特性が確保できないという問題が生
じる。During firing of the external electrodes, the glass softens and flows to the external electrode / internal electrode interface. Ni, which is a component of the internal electrode, is dissolved and diffused in the glass that has become the liquid phase, and is further deposited on the external electrode Cu and diffused inward. Therefore, the tip of the internal electrode disappears, and the internal electrode apparently has a structure retracted inside. As a result, the electrical connection between the internal electrodes and the external electrodes cannot be sufficiently obtained, and the electrical characteristics of the monolithic ceramic electronic component cannot be ensured.
【００１０】ここ近年、電子部品の小型化・高性能化の
要求が高まり、積層セラミックコンデンサにおいても薄
層・多層化がますます進んでいる。それに伴い内部電極
の物理的な厚みが減少していき、上記のような問題がま
すます顕著に発生するようになった。In recent years, there has been an increasing demand for miniaturization and high performance of electronic components, and multilayer ceramic capacitors are becoming thinner and more multilayered. Along with that, the physical thickness of the internal electrodes has decreased, and the above problems have become more prominent.
【００１１】本発明は、上述の問題点を解決するため
に、内部電極と外部電極との機械的・電気的接続を確保
することが可能となる外部電極用の導電性ペーストを用
いて形成した積層セラミック電子部品を提供することを
目的とする。In order to solve the above-mentioned problems, the present invention is formed by using a conductive paste for an external electrode, which can secure mechanical and electrical connection between the internal electrode and the external electrode. An object is to provide a monolithic ceramic electronic component.
【００１２】なお、特開平１１−５４３６８号公報或い
は特開平１１−３４５７４１号公報には、外部電極に主
成分としてＣｕを含有し、さらにＦｅを含むような積層
セラミック電子部品が開示されている。Incidentally, JP-A-11-54368 or JP-A-11-345741 discloses a laminated ceramic electronic component in which the external electrode contains Cu as a main component and further contains Fe.
【００１３】しかし、これら公報に記載の発明の目的
は、外部電極の比抵抗のアップや、セラミックと内部電
極との密着性の向上であり、外部電極と内部電極との接
合性の改善を目的とするものではない。さらに、金属の
Ｆｅを用いた場合、ペースト状態においてはＦｅの酸化
に伴うペースト粘度経時変化、或いは電子部品とした場
合はＦｅの酸化に伴う経時的な特性劣化が発生するとい
う問題がある。However, the objects of the inventions described in these publications are to increase the specific resistance of the external electrode and to improve the adhesion between the ceramic and the internal electrode, and to improve the bondability between the external electrode and the internal electrode. Not meant to be. Further, when metallic Fe is used, there is a problem that in the paste state, the paste viscosity changes with time due to oxidation of Fe, or in the case of an electronic component, characteristic deterioration with time due to oxidation of Fe occurs.
【００１４】[0014]
【課題を解決するための手段】本発明の積層セラミック
電子部品は、上記課題を解決するために、複数のセラミ
ック層を互いに積層して有する積層体と、セラミック層
間に形成された、Ｎｉを主成分とする内部導体と、積層
体の端面に形成され、内部導体と電気的に導通する、Ｃ
ｕを主成分とする外部電極とを備え、内部導体は、外部
電極方向に積層体の端面を超えて突出しており、外部電
極は、導電性ペーストの焼結体であり、該導電性ペース
トは、主成分である銅以外に、ガラスフリットと、焼結
時、内部導体成分であるニッケルの外部電極中への拡散
を抑制し、かつ内部導体中へと拡散する化合物と、を含
むことを特徴としている。In order to solve the above-mentioned problems, a laminated ceramic electronic component of the present invention is mainly composed of a laminated body having a plurality of ceramic layers laminated to each other and Ni formed between the ceramic layers. C, which is formed on the end face of the laminated body and the internal conductor as a component and electrically connects with the internal conductor, C
An external electrode containing u as a main component is provided, the internal conductor projects in the direction of the external electrode beyond the end surface of the laminate, and the external electrode is a sintered body of a conductive paste. In addition to copper as a main component, a glass frit and a compound that suppresses diffusion of nickel, which is an internal conductor component, into the external electrode during sintering and diffuses into the internal conductor are also included. I am trying.
【００１５】上記構成によれば、積層セラミックコンデ
ンサに代表されるセラミック電子部品の内部導体がＮｉ
を主成分とする金属からなり、外部電極がＣｕを主成分
とする金属からなり、内部導体が外部電極方向に積層体
の端面を超えて突出しているので、内部導体と外部電極
との機械的・電気的接続を十分に確保することができ、
セラミック電子部品の所望の電気特性を得ることがで
き、さらにセラミック電子部品の信頼性も確保すること
が可能となる。According to the above structure, the inner conductor of the ceramic electronic component represented by the monolithic ceramic capacitor is Ni.
Since the outer electrode is made of a metal containing Cu as a main component, and the inner conductor projects in the direction of the outer electrode beyond the end face of the laminate, the mechanical strength of the inner conductor and the outer electrode is increased.・ A sufficient electrical connection can be secured,
The desired electrical characteristics of the ceramic electronic component can be obtained, and the reliability of the ceramic electronic component can be ensured.
【００１６】上記構成では、外部電極が導電性ペースト
の焼結体であり、該導電性ペーストは、主成分である銅
以外に、ガラスフリットと、焼結時、内部導体成分であ
るニッケルの外部電極中への拡散を抑制し、かつ内部導
体中へと拡散する化合物と、を含む。このため、外部電
極を焼成により形成するときに、内部導体は、その先端
部の消失を抑制でき、かつ、前記化合物の成分が内部導
体上に析出し、内部へと拡散して内部導体体積が増大
し、外部電極方向に積層体の端面を超えて突出させるこ
とができる。In the above structure, the external electrode is a sintered body of a conductive paste, and the conductive paste contains glass frit and nickel, which is an internal conductor component during sintering, in addition to copper as a main component. A compound that suppresses diffusion into the electrode and diffuses into the inner conductor. Therefore, when the outer electrode is formed by firing, the inner conductor can suppress the disappearance of the tip portion thereof, and the components of the compound are deposited on the inner conductor and diffused into the inside to reduce the inner conductor volume. It is possible to increase the number of protrusions and to protrude beyond the end surface of the laminate in the direction of the external electrode.
【００１７】本発明の他の積層セラミック電子部品は、
前記課題を解決するために、複数のセラミック層を互い
に積層して有する積層体と、セラミック層間に形成され
た、Ｎｉを主成分とする内部導体と、積層体の端面に形
成され、内部導体と電気的に導通する、Ｃｕを主成分と
する外部電極とを備え、外部電極は、導電性ペーストの
焼結体であり、該導電性ペーストは、主成分である銅以
外に、ガラスフリットと、焼結時、内部導体成分である
ニッケルの外部電極中への拡散を抑制し、かつ内部導体
中へと拡散する化合物と、を含むことを特徴としてい
る。Another laminated ceramic electronic component of the present invention is
In order to solve the above-mentioned problems, a laminated body having a plurality of ceramic layers laminated to each other, an internal conductor containing Ni as a main component formed between the ceramic layers, and an internal conductor formed on an end surface of the laminated body, An electrically conductive external electrode containing Cu as a main component is provided, wherein the external electrode is a sintered body of a conductive paste, and the conductive paste is a glass frit in addition to copper as the main component. A compound that suppresses the diffusion of nickel, which is a component of the inner conductor, into the outer electrode during sintering and diffuses into the inner conductor.
【００１８】上記構成によれば、外部電極が導電性ペー
ストの焼結体であり、該導電性ペーストは、主成分であ
る銅以外に、ガラスフリットと、焼結時、内部導体成分
であるニッケルの外部電極中への拡散を抑制し、かつ内
部導体中へと拡散する化合物と、を含む。このため、外
部電極を焼成により形成するときに、内部導体は、その
先端部の消失を抑制でき、かつ、前記化合物の成分が内
部導体上に析出し、内部へと拡散して内部導体体積が増
大し、外部電極方向に積層体の端面を超えて突出させる
ことができる。According to the above construction, the external electrode is a sintered body of a conductive paste, and the conductive paste contains, in addition to copper as a main component, glass frit and nickel as an internal conductor component at the time of sintering. A compound that suppresses the diffusion of the metal into the outer electrode and diffuses into the inner conductor. Therefore, when the outer electrode is formed by firing, the inner conductor can suppress the disappearance of the tip portion thereof, and the components of the compound are deposited on the inner conductor and diffused into the inside to reduce the inner conductor volume. It is possible to increase the number of protrusions and to protrude beyond the end surface of the laminate in the direction of the external electrode.
【００１９】これにより、上記構成は、内部導体と外部
電極との機械的・電気的接続を十分に確保することがで
き、セラミック電子部品の所望の電気特性を得ることが
でき、さらにセラミック電子部品の信頼性も確保するこ
とが可能となる。よって、上記構成は、セラミック電子
部品の信頼性をより確保できる。As a result, the above structure can sufficiently secure the mechanical and electrical connection between the inner conductor and the outer electrode, obtain the desired electrical characteristics of the ceramic electronic component, and further, the ceramic electronic component. It becomes possible to secure the reliability of. Therefore, the above configuration can further secure the reliability of the ceramic electronic component.
【００２０】上記積層セラミック電子部品では、前記化
合物は鉄（Ｆｅ）化合物であることが望ましい。上記構
成によれば、化合物がＦｅ化合物であることによって、
内部導体における、外部電極方向に積層体の端面を超え
た突出をより確実に形成できる。In the above laminated ceramic electronic component, the compound is preferably an iron (Fe) compound. According to the above configuration, the compound is an Fe compound,
It is possible to more reliably form a protrusion in the inner conductor in the direction of the outer electrode beyond the end face of the laminate.
【００２１】上記積層セラミック電子部品においては、
前記Ｆｅ化合物は、Ｆｅ合金粉末であることが好まし
い。上記構成によれば、Ｆｅ化合物がＦｅ合金粉末であ
ることにより、上記内部導体の突出をより確実に形成で
きる。In the above laminated ceramic electronic component,
The Fe compound is preferably Fe alloy powder. According to the above configuration, since the Fe compound is the Fe alloy powder, the protrusion of the internal conductor can be formed more reliably.
【００２２】上記積層セラミック電子部品では、前記Ｆ
ｅ合金粉末は、Ｆｅ−Ｎｉ合金粉末であってもよい。上
記構成によれば、Ｆｅ合金粉末がＦｅ−Ｎｉ合金粉末で
あることにより、上記突出をより確実に形成できる。In the above laminated ceramic electronic component, the F
The e-alloy powder may be Fe-Ni alloy powder. According to the above configuration, since the Fe alloy powder is the Fe—Ni alloy powder, the protrusion can be formed more reliably.
【００２３】上記積層セラミック電子部品においては、
前記Ｆｅ化合物はＦｅレジネートであってもよい。上記
構成によれば、Ｆｅ化合物がＦｅレジネートであること
により、上記突出をより確実に形成できる。In the above laminated ceramic electronic component,
The Fe compound may be Fe resinate. According to the above configuration, since the Fe compound is the Fe resinate, the protrusion can be formed more reliably.
【００２４】上記積層セラミック電子部品では、内部導
体は、静電容量が得られるように配置され、積層セラミ
ックコンデンサを構成していてもよい。上記構成によれ
ば、内部導体は、静電容量が得られるように配置され、
積層セラミックコンデンサを構成しているので、内部電
極と外部電極との接続性が改善された、歩留りの良好な
積層セラミックコンデンサを得ることができる。In the above-mentioned laminated ceramic electronic component, the internal conductors may be arranged so as to obtain electrostatic capacitance, and may constitute a laminated ceramic capacitor. According to the above configuration, the inner conductor is arranged so as to obtain a capacitance,
Since the monolithic ceramic capacitor is configured, it is possible to obtain the monolithic ceramic capacitor having improved yield and improved connectivity between the internal electrode and the external electrode.
【００２５】[0025]
【発明の実施の形態】次に、本発明に係る一つの実施形
態のセラミック電子部品としての積層セラミックコンデ
ンサを挙げ、これについて図１を参照して詳細に説明す
る。BEST MODE FOR CARRYING OUT THE INVENTION Next, a monolithic ceramic capacitor as a ceramic electronic component according to one embodiment of the present invention will be described, which will be described in detail with reference to FIG.
【００２６】図１に示すように、積層セラミックコンデ
ンサ１は、互いに積層されたセラミック層２ａを備え
る、略直方体形状のセラミック素体（積層体）２と、各
セラミック層２ａ間に設けられた内部電極（内部導体）
３と、外部電極４とを有している。さらに、外部電極４
上に、Ｎｉめっき膜５と、Ｓｎめっき膜６とが、この順
にて積層されていることが好ましい。As shown in FIG. 1, a monolithic ceramic capacitor 1 includes a ceramic body (multilayer body) 2 having a substantially rectangular parallelepiped shape, which includes ceramic layers 2a laminated to each other, and an interior provided between the ceramic layers 2a. Electrode (inner conductor)
3 and an external electrode 4. Furthermore, the external electrode 4
It is preferable that the Ni plating film 5 and the Sn plating film 6 are laminated on the top in this order.
【００２７】セラミック素体２は、誘電体材料、例えば
ＢａＴｉＯ3を主成分とする複数のセラミックグリーン
シートが互いに積層され焼成されてなる各セラミック層
２ａを有している。The ceramic body 2 includes a dielectric material, each ceramic layer 2a in which a plurality of ceramic green sheets is formed by firing stacked together mainly composed of BaTiO 3, for example.
【００２８】内部電極３は、所定枚数のセラミックグリ
ーンシート上に形成された内部電極用導電性ペーストが
セラミックグリーンシートとともに同時に焼成されてな
り、それぞれの端縁がセラミック層２ａのいずれかの端
面に露出するように形成されている。内部電極３は、Ｎ
ｉを主成分とした内部電極用導電性ペーストを用いたの
で、Ｎｉを主成分としている。The internal electrodes 3 are formed by simultaneously firing an internal electrode conductive paste formed on a predetermined number of ceramic green sheets together with the ceramic green sheets, and each edge is on one end surface of the ceramic layer 2a. It is formed so as to be exposed. The internal electrode 3 is N
Since the conductive paste for internal electrodes containing i as the main component was used, Ni was the main component.
【００２９】そして、内部電極３は、外部電極４方向に
セラミック素体２の上記端面を超えて突出した、突出部
３ａを有している。このような突出部３ａは、外部電極
４のための、後述する導電性ペーストが焼成されると
き、上記導電性ペーストの成分により、内部電極３の外
部電極４への拡散を低減して内部電極３の先端部の消失
が抑制され、また、上記導電性ペーストの成分が内部電
極３の先端部へ析出し、内部へと拡散して内部電極３の
体積が増大することにより、形成することが可能とな
る。The internal electrode 3 has a protruding portion 3a protruding in the direction of the external electrode 4 beyond the end face of the ceramic body 2. Such protrusions 3 a reduce the diffusion of the internal electrodes 3 to the external electrodes 4 by the components of the above-mentioned conductive paste when the conductive paste for the external electrodes 4 to be described later is fired. 3 can be formed by suppressing the disappearance of the tip portion of No. 3 and by depositing the components of the conductive paste on the tip portion of the internal electrode 3 and diffusing into the inside to increase the volume of the internal electrode 3. It will be possible.
【００３０】よって、上記各内部電極３は、セラミック
層２ａの何れかの端面（辺部）に交互に露出すると共
に、セラミック層２ａ間に互いに離間して対面すること
により、セラミック素体２内において、静電容量を形成
できて、積層セラミックコンデンサを構成するように配
置されていることになる。Therefore, the internal electrodes 3 are alternately exposed on any end surface (side portion) of the ceramic layer 2a, and face each other while being separated from each other between the ceramic layers 2a. In, the capacitor is formed so that it is arranged so as to form a monolithic ceramic capacitor.
【００３１】外部電極４は、セラミック素体２の両端面
に、後述する導電性ペーストがそれぞれ塗布され乾燥さ
れて焼成されてなる一対の厚膜電極であり、セラミック
素体２の両端面にそれぞれ露出した各内部電極３に電気
的かつ機械的に接続されるように形成されている。The external electrodes 4 are a pair of thick-film electrodes formed by applying a conductive paste, which will be described later, to both end faces of the ceramic body 2 and drying and firing the same. It is formed so as to be electrically and mechanically connected to each exposed internal electrode 3.
【００３２】このような外部電極４は、互いの間の絶縁
性を容易に確保できることから、互いに対向し、略平行
となるように配置されていることが望ましい。つまり、
外部電極４は、セラミック素体２における、互いに略平
行に対向する両端面上にそれぞれ形成されていることが
好ましい。この場合、内部電極３がそれぞれ露出した各
面は、上記両端面となる。It is desirable that the external electrodes 4 as described above are arranged so as to face each other and be substantially parallel to each other, because the insulation between them can be easily ensured. That is,
The external electrodes 4 are preferably formed on both end surfaces of the ceramic body 2 that face each other substantially in parallel. In this case, the exposed surfaces of the internal electrodes 3 are the both end surfaces.
【００３３】なお、本発明のセラミック電子部品におけ
るセラミック素体２の形状、材質、内部電極３の形成位
置、枚数、めっき膜５、６の材質、層数等は、上述した
一つの実施形態である積層セラミックコンデンサ１に特
に限定されない。The shape and material of the ceramic body 2, the formation position and number of the internal electrodes 3, the material of the plating films 5 and 6, the number of layers, etc. in the ceramic electronic component of the present invention are the same as those in the above-described embodiment. The monolithic ceramic capacitor 1 is not particularly limited.
【００３４】また、本発明の積層セラミックコンデンサ
１におけるセラミック素体２の材料は、上述の実施形態
に限定されることなく、例えばＰｂＴｉＯ3 系、ＰｂＺ
ｒＯ 3 系等その他の誘電体材料からなっていても構わな
い。また、本発明の積層セラミックコンデンサ１におけ
る内部電極の枚数は、上述の実施形態に限定されない。Further, the monolithic ceramic capacitor of the present invention
The material of the ceramic body 2 in No. 1 is the same as in the above-described embodiment.
Without being limited to, for example, PbTiO 33System, PbZ
rO 3It may be made of other dielectric materials such as
Yes. In addition, in the monolithic ceramic capacitor 1 of the present invention,
The number of internal electrodes to be used is not limited to that in the above embodiment.
【００３５】本発明では、外部電極（端子電極）と電気
的に接合される内部導体を有する積層セラミック電子部
品であれば、本発明を適用でき、そのような積層セラミ
ック電子部品としては、例えば、積層セラミックインダ
クタや、積層セラミック抵抗体が挙げられる。In the present invention, the present invention can be applied to any monolithic ceramic electronic component having an internal conductor that is electrically joined to an external electrode (terminal electrode). As such a monolithic ceramic electronic component, for example, Examples thereof include a laminated ceramic inductor and a laminated ceramic resistor.
【００３６】しかしながら、本発明は、積層セラミック
コンデンサ１のように、セラミック素体２の端面に、多
数（２０以上、より好ましくは４０以上）の内部電極３
が露出し、それぞれの内部電極３と外部電極４とを電気
的に接合する必要があるものに対して、より好適なもの
である。However, according to the present invention, like the monolithic ceramic capacitor 1, a large number (20 or more, more preferably 40 or more) of internal electrodes 3 are provided on the end face of the ceramic body 2.
It is more suitable for those in which the internal electrodes 3 and the external electrodes 4 need to be electrically joined.
【００３７】本発明に用いられる外部電極４用の導電性
ペーストは、Ｃｕを主成分とする導電成分と、ガラスフ
リットと、有機ビヒクルと、Ｆｅ化合物とを含む。さら
に、Ｆｅ化合物はＦｅ合金、或いはＦｅレジネートであ
ることが好ましい。The conductive paste for the external electrode 4 used in the present invention contains a conductive component containing Cu as a main component, a glass frit, an organic vehicle, and an Fe compound. Further, the Fe compound is preferably a Fe alloy or a Fe resinate.
【００３８】Ｆｅは、Ｃｕ或いはＮｉよりもガラス中へ
と溶解しやすい。このため、Ｆｅは外部電極焼成時に軟
化・流動したガラス中へ選択的に溶解する。このため、
ガラス中へのＮｉの溶解を抑制する効果があり、内部電
極３の先端部の消失をある程度抑制することが可能とな
る。Fe is more easily dissolved in glass than Cu or Ni. Therefore, Fe is selectively dissolved in the glass that is softened and fluidized during firing of the external electrode. For this reason,
There is an effect of suppressing the dissolution of Ni in the glass, and it becomes possible to suppress the disappearance of the tip portion of the internal electrode 3 to some extent.
【００３９】さらに、Ｆｅは、内部電極３のＮｉと合金
化し易いため、Ｆｅの一部がＮｉ上に析出、内部へと拡
散して内部電極３の体積が増大し、内部電極３の先端部
が外部電極４方向にセラミック素体２の端面から突き出
した突出部３ａを形成する効果を備えている。これら作
用により、内部電極３と外部電極４との接合がより強固
なものとなり、内部電極３と外部電極４との機械的・電
気的接続を確保することが可能となる。Further, since Fe is easily alloyed with Ni of the internal electrode 3, a part of Fe is deposited on Ni and diffuses into the inside to increase the volume of the internal electrode 3, and the tip portion of the internal electrode 3 is increased. Has the effect of forming the protruding portion 3a protruding from the end surface of the ceramic body 2 in the direction of the external electrode 4. By these actions, the bonding between the internal electrode 3 and the external electrode 4 becomes stronger, and the mechanical / electrical connection between the internal electrode 3 and the external electrode 4 can be secured.
【００４０】ただし、金属のＦｅであるとペースト状態
においてはＦｅの酸化に伴う粘度変化等の不具合を生じ
る。さらに、電子部品が外部に暴露された状態では、温
度或いは湿度の影響を大きく受け、Ｆｅが酸化し、得ら
れた積層セラミック電子部品の信頼性が大きく劣化す
る。However, when metallic Fe is used, in the paste state, problems such as a change in viscosity due to the oxidation of Fe occur. Furthermore, when the electronic component is exposed to the outside, it is greatly affected by temperature or humidity, Fe is oxidized, and the reliability of the obtained monolithic ceramic electronic component is significantly deteriorated.
【００４１】そこで、本発明においてはＦｅの経時的な
酸化を抑制する目的で、耐酸化性を有するＦｅ化合物と
いう形でＦｅを添加することを特徴とする。耐酸化性を
有するＦｅ化合物としては、例えばＦｅ合金、Ｆｅレジ
ネートなどが挙げられる。Therefore, the present invention is characterized in that Fe is added in the form of a Fe compound having oxidation resistance for the purpose of suppressing the oxidation of Fe over time. Examples of the Fe compound having oxidation resistance include Fe alloys and Fe resinates.
【００４２】Ｆｅ化合物としてＦｅ酸化物も考えられる
が、Ｆｅ酸化物では本発明の目的を達成しない。これは
Ｆｅ酸化物を用いた場合、ガラス中からの還元、内部電
極上へのＦｅの析出が起こりにくくなり、外部電極４と
内部電極３との接続が十分に得られないためである。An Fe oxide may be used as the Fe compound, but the Fe oxide does not achieve the object of the present invention. This is because when the Fe oxide is used, reduction from the glass and precipitation of Fe on the internal electrodes are less likely to occur, and the connection between the external electrode 4 and the internal electrode 3 cannot be sufficiently obtained.
【００４３】なお、上記導電性ペーストでは、導電成分
に対するガラスフリットの比率については特に限定され
るものではないが、導電成分に対し２重量％〜２０重量
％の範囲内にあることが好ましい。ガラスフリット比率
が２重量％を下回ると、本発明の効果が得られにくい。
一方、ガラスフリット比率が２０重量％を上回ると、外
部電極表面ヘガラスが染み出し、めっきが付きにくいな
どの不具合を生じる。In the conductive paste, the ratio of glass frit to the conductive component is not particularly limited, but it is preferably in the range of 2% by weight to 20% by weight with respect to the conductive component. If the glass frit ratio is less than 2% by weight, it is difficult to obtain the effects of the present invention.
On the other hand, when the glass frit ratio exceeds 20% by weight, the glass is exuded on the surface of the external electrode, which causes problems such as difficulty in plating.
【００４４】[0044]
【実施例】以下、本発明の実施例について説明する。今
回、評価に用いた試料を表１に示す。試料番号１〜３は
比較例であり、試料番号４〜６は実施例である。EXAMPLES Examples of the present invention will be described below. Table 1 shows the samples used for evaluation this time. Sample numbers 1 to 3 are comparative examples, and sample numbers 4 to 6 are examples.
【００４５】[0045]
【表１】 [Table 1]
【００４６】上記表1では、○は良、×は不可を示し、
Ｃａｐは静電容量を示す。In Table 1 above, ○ means good, × means bad,
Cap indicates capacitance.
【００４７】まず、ガラスフリットを以下の通り作製し
た。目的のガラスフリットになるように出発原料を調合
し、１０００℃〜１２００℃で溶融させた後、急冷して
ガラス化した。その後、得られたガラスを粗粉砕、微粉
砕して所望の粒度分布のガラスフリットを得た。本評価
にはホウケイ酸亜鉛バリウム系ガラスを用いた。ガラス
フリットの平均粒径は０．５μｍのものを用いた。First, a glass frit was prepared as follows. The starting materials were mixed so as to obtain the desired glass frit, melted at 1000 ° C to 1200 ° C, and then rapidly cooled to vitrify. Then, the obtained glass was coarsely pulverized and finely pulverized to obtain a glass frit having a desired particle size distribution. Zinc barium borosilicate glass was used for this evaluation. A glass frit having an average particle size of 0.5 μm was used.
【００４８】次に、上記ガラスフリットを用いて導電性
ペーストを作製した。本実施例においては、導電成分の
粉末を７０重量％、ガラスフリットを６重量％、有機ビ
ヒクルを２４重量％混合し、三本ロールで混練・分散し
て、表１の試料番号１〜５に示した導電性ペーストを５
種類得た。Next, a conductive paste was prepared using the above glass frit. In this example, 70% by weight of conductive component powder, 6% by weight of glass frit and 24% by weight of organic vehicle were mixed and kneaded and dispersed by a three-roll to give sample numbers 1 to 5 in Table 1. The conductive paste shown is 5
Got the kind.
【００４９】また、試料番号６については、導電成分の
粉末を６５重量％、ガラスフリットを６重量％、有機ビ
ヒクルを２４重量％、Ｆｅレジネートを５重量％となる
ように混合し、作製した。使用した導電粉末の主成分は
Ｃｕ粉であり、平均粒径２μｍのものを用いた。Sample No. 6 was prepared by mixing the conductive component powder in an amount of 65% by weight, the glass frit in an amount of 6% by weight, the organic vehicle in an amount of 24% by weight, and the Fe resinate in an amount of 5% by weight. The main component of the conductive powder used was Cu powder, and the average particle size was 2 μm.
【００５０】試料番号２〜５に関しては導電成分の粉末
中にＣｕ以外の金属粉末を５重量％添加した。添加した
金属粉末の平均粒径はいずれも３μｍである。有機ビヒ
クルは主にアクリル樹脂からなる有機バインダを、主に
テルピネオールからなる有機溶剤に溶解させたものを用
いた。For Sample Nos. 2 to 5, 5% by weight of metal powder other than Cu was added to the powder of the conductive component. The average particle size of the added metal powder is 3 μm. The organic vehicle used was one in which an organic binder mainly made of acrylic resin was dissolved in an organic solvent mainly made of terpineol.
【００５１】得られた試料番号１〜６の導電性ペースト
についてペースト粘度経時変化の調査を行った。得られ
た結果を表１にまとめた。表１に示す数字はペースト作
製直後から１ヶ月後のペースト粘度変化率を示す。ペー
スト粘度はＥ型粘度計により測定を行い、測定条件は１
ｒｐｍ、２５℃とした。表にはｎ＝３の平均値を示し
た。ペースト粘度経時変化率が小さいほど安定した外部
電極形状、外部電極品質（めっきの付き回りなど）が得
られ、良好な導電性ペーストといえる。With respect to the obtained conductive pastes of Sample Nos. 1 to 6, the change in paste viscosity with time was investigated. The results obtained are summarized in Table 1. The numbers shown in Table 1 show the rate of change in paste viscosity immediately after the paste was prepared and one month later. The paste viscosity is measured with an E-type viscometer, and the measurement condition is 1
rpm and 25 ° C. The table shows the average value of n = 3. The smaller the paste viscosity change over time, the more stable the shape of the external electrode and the quality of the external electrode (such as the plating coverage) can be obtained, and it can be said that this is a good conductive paste.
【００５２】表１より、金属のＦｅを添加した試料番号
２は、導電性ペーストの粘度変化が２０％以上と非常に
大きくなった。表中には示していないが、このため、Ｎ
ｉめっき膜５、Ｓｎめっき膜６が部分的に付かなくなる
という不具合が生じた。これに対し、試料番号１及び３
〜６の試料はペースト粘度変化が±２％以内と安定して
おり、特に粘度変化に伴う不具合等は生じなかった。From Table 1, in the case of Sample No. 2 in which metallic Fe was added, the change in viscosity of the conductive paste was 20% or more, which was very large. Although not shown in the table, N
The i-plated film 5 and the Sn-plated film 6 are partially left unattached. In contrast, sample numbers 1 and 3
The samples of Nos. 6 to 6 had a stable paste viscosity change of ± 2% or less, and did not cause any problems with the viscosity change.
【００５３】次に、ＢａＴｉＯ3を主成分とするセラミ
ックグリーンシートを作製し、所定枚数のセラミックグ
リーンシートの表面上に一方の端縁がセラミックグリー
ンシートの何れかの端面側に露出するように、内部電極
となるべき、Ｎｉを主成分とする内部電極用導電性ペー
ストを印刷した。続いて、これらセラミックグリーンシ
ートを１００枚、それらの厚さ方向に互いに積層し圧着
して、複数の生のセラミック素体を作製した。これらを
還元雰囲気中、１２００℃〜１４００℃で焼成し、前記
の内部電極３を備えた焼結体であるセラミック素体２を
得た。Next, a ceramic green sheet containing BaTiO 3 as a main component is prepared, and one edge of the ceramic green sheet is exposed on the surface of a predetermined number of the ceramic green sheets so as to be exposed on either side of the ceramic green sheet. A conductive paste for internal electrodes, which contains Ni as a main component and is to be internal electrodes, was printed. Then, 100 sheets of these ceramic green sheets were laminated on each other in the thickness direction and pressure-bonded to produce a plurality of raw ceramic bodies. These were fired in a reducing atmosphere at 1200 ° C to 1400 ° C to obtain a ceramic body 2 that was a sintered body having the internal electrodes 3 described above.
【００５４】次に、得られたセラミック素体２の両端面
に試料番号１〜６の導電性ペーストを浸漬塗布し、１２
０℃で１０分間乾燥した後、Ｎ2−Ｏ2雰囲気（ＰO2３０
０ｐｐｍ以下）中で、８５０℃×１０分ピークの条件下
で焼成して外部電極４をそれぞれ形成した。さらに、得
られた外部電極４上に電解めっき処理によりＮｉめっき
膜５を形成し、その上にＳｎめっき膜６を形成し、試料
番号１〜６の外部電極を有する積層セラミックコンデン
サを得た。Next, the conductive pastes of Sample Nos. 1 to 6 were dip-coated on both end faces of the obtained ceramic body 2, and 12
After drying at 0 ° C. for 10 minutes, an N 2 —O 2 atmosphere (P O2 30
(0 ppm or less), the external electrodes 4 were formed by firing under the conditions of a peak of 850 ° C. for 10 minutes. Further, a Ni plating film 5 was formed on the obtained external electrode 4 by electrolytic plating treatment, and a Sn plating film 6 was formed thereon to obtain multilayer ceramic capacitors having external electrodes of sample numbers 1 to 6.
【００５５】得られた試料番号１〜６の積層セラミック
コンデンサについて静電容量の測定を行った。得られた
結果を表１にまとめた。静電容量はＬＣＲメータにより
測定を行い、表１にはｎ＝２０の平均値を示した。静電
容量値が小さいものほど外部電極４と内部電極３との電
気的接合がとれていないことを示す。本実施例で用いた
積層セラミックコンデンサの設計静電容量は１０μＦで
ある。The capacitance of the obtained laminated ceramic capacitors of Sample Nos. 1 to 6 was measured. The results obtained are summarized in Table 1. The capacitance was measured by an LCR meter, and Table 1 shows the average value of n = 20. The smaller the capacitance value is, the less electrical connection between the outer electrode 4 and the inner electrode 3 is. The design capacitance of the multilayer ceramic capacitor used in this example is 10 μF.
【００５６】表１から明らかなように、試料番号４〜６
の電極を用いた積層セラミックコンデンサは、静電容量
値が１０．２μＦ〜１０．５μＦと設計静電容量値を確
保することができた。また、Ｆｅを添加した試料番号２
についても静電容量値が１０．５μＦと設計静電容量値
を確保することができた。これに対し、試料番号１、試
料番号３は設計静電容量を得ることができなかった。As is clear from Table 1, sample numbers 4 to 6
The multilayer ceramic capacitor using the electrode of No. 2 had a capacitance value of 10.2 μF to 10.5 μF, which was a design capacitance value. Also, sample number 2 with Fe added
Also, the capacitance value of 10.5 μF, which is the designed capacitance value, could be secured. On the other hand, sample Nos. 1 and 3 could not obtain the designed capacitance.
【００５７】得られた積層セラミックコンデンサを切断
し、その断面を研磨して内部電極と外部電極との接合面
を観察したところ、試料番号１に関しては内部電極先端
部の消失が激しく、また試料番号３に関しては内部電極
先端部の消失は比較的進んでいないものの試料番号４〜
６と比較すると、内部電極の外部電極方向への突き出し
がみられない。このため外部電極とのコンタクトがとれ
ず、設計静電容量値を確保することができなかったもの
と思われる。When the obtained monolithic ceramic capacitor was cut and the cross section thereof was polished and the joint surface between the internal electrode and the external electrode was observed, the sample No. 1 showed a sharp disappearance of the internal electrode tip and the sample No. For sample 3, the disappearance of the tip of the internal electrode has not progressed relatively, but sample number 4 to
Compared with No. 6, no protrusion of the internal electrode toward the external electrode was observed. Therefore, it is considered that the designed capacitance value could not be secured because the contact with the external electrode could not be established.
【００５８】また、試料番号１〜６の積層セラミックコ
ンデンサについて信頼性評価を行った。積層コンデンサ
を８５℃、９５ＲＨ％に保たれた恒温恒湿槽中に１００
時間放置し、その後、それらサンプルの静電容量の測定
および外部電極部の外観観察を行った。判定結果を表１
に示す。試料番号２においては静電容量が約１０％低下
し、さらに外部電極内部まで酸化の進行がみられたた
め、判定としては表１中に示すように×として他と区別
した。Further, reliability evaluation was performed on the laminated ceramic capacitors of sample numbers 1 to 6. Place the multilayer capacitor in a thermo-hygrostat at 85 ℃ and 95RH%
After leaving for a time, the capacitance of these samples was measured and the external electrodes were observed for appearance. Table 1 shows the judgment results
Shown in. In Sample No. 2, the electrostatic capacity was reduced by about 10%, and further the oxidation progressed to the inside of the external electrode. Therefore, as shown in Table 1, the judgment was made as x to distinguish it from the others.
【００５９】[0059]
【発明の効果】本発明の積層セラミック電子部品は、積
層体の端面に形成され、内部導体と電気的に導通する、
銅を主成分とする外部電極を備え、内部導体は、外部電
極方向に積層体の端面から突出している構成である。The monolithic ceramic electronic component of the present invention is formed on the end face of a laminated body and electrically connected to the internal conductor.
An external electrode containing copper as a main component is provided, and the internal conductor is configured to project from the end surface of the laminate in the external electrode direction.
【００６０】それゆえ、上記構成は、内部電極がＮｉを
主成分とする金属からなり、外部電極がＣｕを主成分と
する金属からなりガラスフリットを含有する場合におい
て、内部電極と外部電極との機械的・電気的接続を、上
記突出によって、十分に確保することができる。Therefore, in the above structure, when the internal electrode is made of a metal containing Ni as a main component and the external electrode is made of a metal containing Cu as a main component and contains a glass frit, the internal electrode and the external electrode are Mechanical and electrical connection can be sufficiently secured by the protrusion.
【００６１】これにより、上記構成は、積層セラミック
電子部品において、所望の電気特性を得ることができ、
さらに積層セラミック電子部品の信頼性も確保すること
が可能となるという効果を奏する。As a result, the above structure can obtain desired electric characteristics in the multilayer ceramic electronic component,
Further, it is possible to secure the reliability of the monolithic ceramic electronic component.
【図１】本発明の積層コンデンサを示す概略断面図であ
る。FIG. 1 is a schematic sectional view showing a multilayer capacitor of the present invention.
２ セラミック素体 ２ａ セラミック層 ３ 内部電極 ３ａ 突出部 ４ 外部電極 ５ Ｎｉめっき ６ Ｓｎめっき 2 Ceramic body 2a Ceramic layer 3 internal electrodes 3a protrusion 4 external electrodes 5 Ni plating 6 Sn plating
フロントページの続き Ｆターム(参考） 5E082 AB03 BC32 EE04 EE11 EE23 EE35 FG06 FG26 FG54 GG10 GG11 GG28 JJ03 JJ12 JJ23Continued front page F-term (reference) 5E082 AB03 BC32 EE04 EE11 EE23 EE35 FG06 FG26 FG54 GG10 GG11 GG28 JJ03 JJ12 JJ23
Claims (7)
る積層体と、 セラミック層間に形成された、ニッケルを主成分とする
内部導体と、 積層体の端面に形成され、内部導体と電気的に導通す
る、銅を主成分とする外部電極とを備え、 内部導体は、外部電極方向に積層体の端面を超えて突出
しており、 外部電極は、導電性ペーストの焼結体であり、 該導電性ペーストは、主成分である銅以外に、ガラスフ
リットと、焼結時、内部導体成分であるニッケルの外部
電極中への拡散を抑制し、かつ内部導体中へと拡散する
化合物と、を含むことを特徴とする積層セラミック電子
部品。1. A laminate having a plurality of ceramic layers laminated to each other, an internal conductor containing nickel as a main component formed between the ceramic layers, and an internal conductor formed on an end surface of the laminate and electrically connected to the internal conductor. A conductive external electrode mainly composed of copper, the internal conductor protruding in the direction of the external electrode beyond the end surface of the laminate, and the external electrode being a sintered body of a conductive paste. The conductive paste contains, in addition to copper as a main component, a glass frit and a compound that suppresses diffusion of nickel, which is an internal conductor component, into an external electrode during sintering and diffuses into the internal conductor. A monolithic ceramic electronic component characterized by the above.
体と、 セラミック層間に形成された、ニッケルを主成分とする
内部導体と、 積層体の端面に形成され、内部導体と電気的に導通す
る、銅を主成分とする外部電極とを備え、 外部電極は、導電性ペーストの焼結体であり、 該導電性ペーストは、主成分である銅以外に、ガラスフ
リットと、焼結時、内部導体成分であるニッケルの外部
電極中への拡散を抑制し、かつ内部導体中へと拡散する
化合物と、を含むことを特徴とする積層セラミック電子
部品。2. A laminated body having a plurality of laminated ceramic layers, an internal conductor containing nickel as a main component, formed between the ceramic layers, and electrically connected to the internal conductor formed on an end face of the laminated body. And an external electrode containing copper as a main component, wherein the external electrode is a sintered body of a conductive paste, and the conductive paste contains a glass frit in addition to copper, which is a main component, at the time of sintering. A multilayer ceramic electronic component comprising: a compound that suppresses diffusion of nickel, which is a component of an internal conductor, into an external electrode and that diffuses into the internal conductor.
する請求項１又は２記載の積層セラミック電子部品。3. The multilayer ceramic electronic component according to claim 1, wherein the compound is an iron compound.
特徴とする請求項３に記載の積層セラミック電子部品。4. The multilayer ceramic electronic component according to claim 3, wherein the iron compound is iron alloy powder.
であることを特徴とする請求項４に記載の積層セラミッ
ク電子部品。5. The monolithic ceramic electronic component according to claim 4, wherein the iron alloy powder is iron-nickel alloy powder.
特徴とする請求項３に記載の積層セラミック電子部品。6. The monolithic ceramic electronic component according to claim 3, wherein the iron compound is iron resinate.
置され、積層セラミックコンデンサを構成していること
を特徴とする請求項１乃至６の何れか１項に記載の積層
セラミック電子部品。7. The monolithic ceramic electronic component according to claim 1, wherein the inner conductors are arranged so as to obtain a capacitance, and form a monolithic ceramic capacitor. .
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|---|---|---|---|---|
| JP2006108189A (en) * | 2004-09-30 | 2006-04-20 | Nippon Chemicon Corp | Laminated ceramic capacitor manufacturing method |
| JP2010027730A (en) * | 2008-07-16 | 2010-02-04 | Tdk Corp | Ceramic multilayer electronic component and manufacturing method thereof |
| CN102290235A (en) * | 2010-05-27 | 2011-12-21 | 株式会社村田制作所 | Ceramic electronic component and method for manufacturing the same |
| WO2014175034A1 (en) * | 2013-04-25 | 2014-10-30 | 株式会社村田製作所 | Multi-layer ceramic capacitor and method for manufacturing same |
| CN107331508A (en) * | 2016-04-21 | 2017-11-07 | Tdk株式会社 | Electronic unit |
| JP2021019008A (en) * | 2019-07-17 | 2021-02-15 | 株式会社村田製作所 | Electronic component |
| JP2021040044A (en) * | 2019-09-03 | 2021-03-11 | 株式会社村田製作所 | Electronic component and manufacturing method thereof |
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| KR20130111000A (en) * | 2012-03-30 | 2013-10-10 | 삼성전기주식회사 | Laminated ceramic electronic parts and fabricating method thereof |
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|---|---|---|---|---|
| JP2006108189A (en) * | 2004-09-30 | 2006-04-20 | Nippon Chemicon Corp | Laminated ceramic capacitor manufacturing method |
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| JP5904305B2 (en) * | 2013-04-25 | 2016-04-13 | 株式会社村田製作所 | Multilayer ceramic capacitor and manufacturing method thereof |
| WO2014175034A1 (en) * | 2013-04-25 | 2014-10-30 | 株式会社村田製作所 | Multi-layer ceramic capacitor and method for manufacturing same |
| US9842698B2 (en) | 2013-04-25 | 2017-12-12 | Murata Manufacturing Co., Ltd. | Multilayer ceramic capacitor and manufacturing method therefor |
| CN107331508A (en) * | 2016-04-21 | 2017-11-07 | Tdk株式会社 | Electronic unit |
| CN107331508B (en) * | 2016-04-21 | 2019-07-02 | Tdk株式会社 | Electronic component |
| JP2021019008A (en) * | 2019-07-17 | 2021-02-15 | 株式会社村田製作所 | Electronic component |
| JP7226161B2 (en) | 2019-07-17 | 2023-02-21 | 株式会社村田製作所 | electronic components |
| JP2021040044A (en) * | 2019-09-03 | 2021-03-11 | 株式会社村田製作所 | Electronic component and manufacturing method thereof |
| JP7226198B2 (en) | 2019-09-03 | 2023-02-21 | 株式会社村田製作所 | Electronic component and its manufacturing method |
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