JP2000252158A - Multilayer ceramic capacitor - Google Patents
Multilayer ceramic capacitorInfo
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- JP2000252158A JP2000252158A JP11050250A JP5025099A JP2000252158A JP 2000252158 A JP2000252158 A JP 2000252158A JP 11050250 A JP11050250 A JP 11050250A JP 5025099 A JP5025099 A JP 5025099A JP 2000252158 A JP2000252158 A JP 2000252158A
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- Prior art keywords
- powder
- internal electrode
- multilayer ceramic
- capacitor
- ceramic capacitor
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- Fixed Capacitors And Capacitor Manufacturing Machines (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、積層セラミックコ
ンデンサに関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a multilayer ceramic capacitor.
【０００２】[0002]
【従来技術】近年、積層セラミックコンデンサの内部電
極層としてＡｇ−Ｐｄ合金が使用されているが、最近の
低コスト化に対応するために、内部電極層にＮｉ、Ｃｕ
などの卑金属材料が使用されるようになっている。この
Ｎｉ、Ｃｕなどの卑金属は酸化され易い材料であるた
め、特に内部電極層の形成工程にあたり、また、形成し
た後の工程、例えば外部電極の形成工程で、内部電極層
の酸化を防止するため、低酸素濃度（１０-8〜１０-12
ａｔｍ）雰囲気で焼成していた。2. Description of the Related Art In recent years, an Ag--Pd alloy has been used as an internal electrode layer of a multilayer ceramic capacitor. However, in order to cope with recent cost reduction, Ni or Cu is used for the internal electrode layer.
Such base metal materials are used. Since the base metal such as Ni or Cu is a material that is easily oxidized, it is used to prevent the oxidation of the internal electrode layer particularly in the step of forming the internal electrode layer and in the step after formation, for example, in the step of forming the external electrode. , Low oxygen concentration (10 -8 to 10 -12
atm) It was fired in an atmosphere.
【０００３】内部電極層の材料としてＮｉ、Ｃｕなどの
卑金属材料を用いた積層セラミックコンデンサの外部電
極として、従来、銅ペーストの焼き付けて形成した外部
端子からなるものが知られている。このような積層セラ
ミックコンデンサにおける銅の焼き付け電極（外部端
子）は、銅粉末５５〜８０重量％と、ガラスフリット５
〜２０重量％と、有機ビヒクル１０〜３０重量％とから
なる銅ペーストを塗布し、弱還元雰囲気中８００℃、３
０分の条件で焼き付けて形成されていた（例えば、特公
平８−４０５５号公報参照）。Conventionally, as an external electrode of a multilayer ceramic capacitor using a base metal material such as Ni or Cu as a material of an internal electrode layer, an external electrode formed by baking a copper paste is known. In such a multilayer ceramic capacitor, a copper baked electrode (external terminal) comprises 55 to 80% by weight of copper powder and 5% by weight of glass frit.
To 20% by weight and 10 to 30% by weight of an organic vehicle, and then applied at 800 ° C. in a weak reducing atmosphere.
It was formed by baking under the condition of 0 minutes (for example, see Japanese Patent Publication No. 8-4055).
【０００４】このような積層セラミックコンデンサで
は、銅ペースト中のガラスフリット成分により、誘電体
磁器層と内部電極層からなるコンデンサ本体の一端に外
部端子を十分な強度で固着することができる。In such a multilayer ceramic capacitor, an external terminal can be fixed with sufficient strength to one end of a capacitor body composed of a dielectric ceramic layer and an internal electrode layer by a glass frit component in a copper paste.
【０００５】[0005]
【発明が解決しようとする課題】しかしながら、従来の
積層セラミックコンデンサでは、外部端子の厚みが、例
えば６０〜１００μｍと厚いため、外部端子の形成工程
で、上述のような低酸素濃度で且つ８００℃とういう高
温で焼き付け処理を行って脱バインダー処理しても外部
端子中の炭素を完全に飛散させることができずに、外部
端子中に炭素が残存し、この結果、誘電体磁器層が還元
され、誘電体磁器層の特性が変化してしまい、特に、コ
ンデンサとしての絶縁抵抗値が低下してしまうという致
命的な問題を誘発してしまう。However, in the conventional multilayer ceramic capacitor, since the external terminals have a thickness of, for example, 60 to 100 μm, the external terminals are formed at a low oxygen concentration and 800 ° C. Even if the baking process is performed at a high temperature to remove the binder, the carbon in the external terminals cannot be completely scattered, and the carbon remains in the external terminals.As a result, the dielectric ceramic layer is reduced. In addition, the characteristics of the dielectric porcelain layer are changed, and in particular, a fatal problem that the insulation resistance value of the capacitor is reduced is induced.
【０００６】絶縁抵抗値が低下してしまった積層セラミ
ックコンデンサにおいては、絶縁抵抗値を回復するため
に、例えば、高い酸素濃度雰囲気で熱処理して酸素を補
うことが考えられる。例えば、コンデンサ本体の作製後
の熱処理工程である外部端子の焼き付け工程において高
い酸素分圧で焼成処理を行うと、外部端子を通して内部
電極層が酸化され、内部電極層と外部端子との導通がと
れず、静電容量がバラツクという問題があった。結局、
外部端子は低い酸素分圧で焼き付けせざるを得ず、誘電
体磁器層の絶縁抵抗値の改善は困難であった。In order to recover the insulation resistance value of the multilayer ceramic capacitor whose insulation resistance value has been reduced, it is conceivable to supplement the oxygen by, for example, performing a heat treatment in a high oxygen concentration atmosphere. For example, when a baking treatment is performed at a high oxygen partial pressure in a baking step of an external terminal, which is a heat treatment step after the production of the capacitor body, the internal electrode layer is oxidized through the external terminal, and conduction between the internal electrode layer and the external terminal is reduced. However, there is a problem that the capacitance varies. After all,
The external terminals had to be baked at a low oxygen partial pressure, and it was difficult to improve the insulation resistance of the dielectric ceramic layer.
【０００７】一方、磁器の還元を防止するために、低温
で（例えば７００℃）Ｃｕを含有する端子用導電性ペー
ストの焼き付けを行うことが考えられるが、従来の端子
用導電性ペーストではＣｕとガラスとの濡れ性が低いた
め、外部端子の緻密性が低下してしまうという問題があ
った。On the other hand, in order to prevent the reduction of the porcelain, it is conceivable to bake the terminal-containing conductive paste containing Cu at a low temperature (for example, 700 ° C.). Since the wettability with glass is low, there is a problem that the denseness of the external terminal is reduced.
【０００８】即ち、端子用導電性ペーストではＣｕとガ
ラスとの濡れ性が低いため、図５に示すように、外部端
子１１の表面にガラス相が析出してガラス膜１２を形成
してしまう。このガラス膜１２の存在により、外部端子
１１の表面にメッキ膜を形成することが困難となる。こ
れによりハンダによる基板等への接続が困難となる。That is, since the terminal conductive paste has low wettability between Cu and glass, a glass phase is deposited on the surface of the external terminal 11 to form the glass film 12 as shown in FIG. The presence of the glass film 12 makes it difficult to form a plating film on the surface of the external terminal 11. This makes it difficult for solder to connect to a substrate or the like.
【０００９】尚、外部端子表面のガラス膜を研摩、もし
くは酸処理して除去して表面メッキ処理を施すことが考
えられるが、外部端子１１は空孔が多くなって緻密性が
低下し、これにより、ハンダ濡れ性を向上するためのメ
ッキ処理時に、メッキ液が外部端子１１内の空孔を介し
て内部電極層１４に浸入し、積層セラミックコンデンサ
をハンダにより基板等に固着する際の加熱によりコンデ
ンサ本体１５に割れ等が生じるという問題があった。
尚、図５において、１３は誘電体材料からなる誘電体磁
器層である。It is conceivable that the surface of the external terminal 11 is polished or acid-treated to remove the glass film, and then subjected to surface plating. Accordingly, during plating treatment for improving solder wettability, a plating solution infiltrates the internal electrode layer 14 through holes in the external terminals 11 and is heated by fixing the multilayer ceramic capacitor to a substrate or the like by soldering. There was a problem that the capacitor body 15 was cracked.
In FIG. 5, reference numeral 13 denotes a dielectric ceramic layer made of a dielectric material.
【００１０】また、特開平２−１５０００７号公報にお
いては、Ｎｉ粉末とＡｇ粉末とＺｎ粉末とガラスフリッ
トとから成る外部端子の材料を大気中で処理することが
開示されているが、この場合、Ａｇ−Ｚｎの合金を形成
し、低融点化を起こす。また、外部端子の厚みを薄くす
ると膜切れを発生しコンデンサ本体を露出してしまい、
コンデンサ本体に割れ等が生じてしまう。即ち、特開平
２−１５０００７号公報の積層セラミックコンデンサで
は、外部端子の厚みを６０〜１００μｍと厚くしない
と、耐熱衝撃性・機械的強度を満足しないものであっ
た。Japanese Unexamined Patent Publication (Kokai) No. 2-150007 discloses that an external terminal material composed of Ni powder, Ag powder, Zn powder and glass frit is treated in the air. An alloy of Ag-Zn is formed to lower the melting point. Also, if the thickness of the external terminals is reduced, the film will break and the capacitor body will be exposed,
Cracks and the like occur in the capacitor body. That is, in the multilayer ceramic capacitor disclosed in Japanese Patent Application Laid-Open No. 2-150007, the thermal shock resistance and the mechanical strength are not satisfied unless the thickness of the external terminals is increased to 60 to 100 μm.
【００１１】その結果、積層セラミックコンデンサ全体
の寸法の規制と上述の外部端子の厚みが厚くなることに
より、コンデンサ本体１５を大きくすることができず、
小型大容量コンデンサを作成するには不利であった。As a result, the size of the capacitor body 15 cannot be increased due to the restriction on the dimensions of the entire multilayer ceramic capacitor and the increase in the thickness of the above-mentioned external terminals.
It was disadvantageous for making a small and large-capacity capacitor.
【００１２】本発明は、上述の問題点に鑑みて案出され
たものであり、その目的は、外部端子の緻密性を向上で
き、卑金属の内部電極層を有するコンデンサ本体に、６
０μｍ以下の厚みの外部端子を形成しても、コンデンサ
本体に割れ等が生じることがない、耐熱衝撃性に優れ、
機械的強度に優れた積層セラミックコンデンサを提供す
ることを目的とする。The present invention has been devised in view of the above-mentioned problems, and an object of the present invention is to provide a capacitor body having a base metal internal electrode layer which can improve the fineness of external terminals.
Even if an external terminal having a thickness of 0 μm or less is formed, the capacitor body does not crack or the like, and has excellent thermal shock resistance,
An object of the present invention is to provide a multilayer ceramic capacitor having excellent mechanical strength.
【００１３】[0013]
【課題を解決するための手段】本発明は、卑金属からな
る内部電極層と誘電体磁器層を交互に積層してなるコン
デンサ本体の両端部に、１０〜９０体積％のＡｇ相と、
Ｎｉ及びＮｉ合金相とか成る外部端子を具備した積層セ
ラミックコンデンサである。According to the present invention, a 10 to 90% by volume Ag phase is provided at both ends of a capacitor body in which internal electrode layers made of a base metal and dielectric ceramic layers are alternately laminated.
This is a multilayer ceramic capacitor provided with external terminals composed of Ni and a Ni alloy phase.
【００１４】なお、このような外部端子は、Ｎｉ粉末ま
たはＮｉ合金末と、Ａｇ粉末と、ガラスフリットと、有
機ビヒクルとから成る外部端子用導電性ペーストを用い
て、コンデンサ本体の端部に塗布し、焼き付け処理する
ことにより形成される。この時、Ｎｉ粉末またはＮｉ合
金末とＡｇ粉末とからなる金属粉末中、銀粉末を１０〜
９０重量％含有させる。The external terminals are coated on the ends of the capacitor body using a conductive paste for external terminals comprising Ni powder or Ni alloy powder, Ag powder, glass frit, and organic vehicle. And formed by baking. At this time, in the metal powder composed of the Ni powder or Ni alloy powder and the Ag powder, the silver powder was
90% by weight.
【００１５】[0015]
【作用】本発明によれば、Ｎｉ系（Ｎｉ単体またはＮｉ
合金）粉末と、Ａｇ粉末と、ガラスフリットと、有機ビ
ヒクルとからなる外部端子用導電性ペーストをもちいて
いる。このよような外部端子用導電性ペーストを卑金属
の内部電極層を有するコンデンサ本体に焼き付け処理し
た場合、Ｎｉ系粉末とＡｇ粉末は反応が無いため、従来
のように、Ａｇ粉末が他の金属などと激しく合金を形成
することがなく、Ｎｉ系粉末と銀粉末とが単に接触した
状態で外部端子の金属成分を構成する。このＡｇ粉末に
より端子電極の焼結性が上がり８００℃以下の比較的低
い焼成温度でも緻密性が向上する。また、Ａｇ粉末とＮ
ｉ粉末は反応が無いため、Ａｇ金属の性質によりたわみ
強度が向上する。According to the present invention, Ni-based (Ni alone or Ni-based)
Alloy) A conductive paste for external terminals is used which is composed of powder, Ag powder, glass frit, and an organic vehicle. When such a conductive paste for external terminals is baked on a capacitor body having a base metal internal electrode layer, the Ni-based powder and the Ag powder do not react with each other. The metal component of the external terminal is formed in a state where the Ni-based powder and the silver powder are simply in contact with each other without violently forming an alloy. The Ag powder improves the sinterability of the terminal electrode and improves the compactness even at a relatively low firing temperature of 800 ° C. or less. Ag powder and N
Since the i-powder has no reaction, the bending strength is improved by the properties of the Ag metal.
【００１６】そして、Ｎｉ系外部端子に、Ａｇ相が安定
的に存在し、且つ均一に分散させることができる。この
Ａｇ相は、外部端子に１０〜９０体積％存在する。これ
により、Ｎｉ粒子間にＡｇ相を確実に存在させることが
でき、外部端子の緻密性が向上する。従って、外部端子
の表面にハンダ濡れ性を向上するためのメッキ処理を施
しても、メッキ液が外部端子中に浸入することがなく、
さらに、内部電極層にも浸入しない。The Ag phase is stably present in the Ni-based external terminal and can be uniformly dispersed. This Ag phase is present at 10 to 90% by volume in the external terminal. As a result, the Ag phase can be reliably present between the Ni particles, and the denseness of the external terminal is improved. Therefore, even when plating is performed on the surface of the external terminal to improve solder wettability, the plating solution does not enter the external terminal,
Furthermore, it does not penetrate into the internal electrode layers.
【００１７】また、積層セラミックコンデンサをハンダ
によりプリント配線基板等に接合しても、ハンダ溶融加
熱で、コンデンサ本体に割れ等が生じることがない。即
ち、耐熱衝撃性に優れた積層セラミックコンデンサとな
り、たわみ強度によりプリント配線基板等にハンダ接合
性が向上する積層セラミックコンデンサとなる。Further, even when the multilayer ceramic capacitor is joined to a printed wiring board or the like by soldering, cracking or the like does not occur in the capacitor body due to solder melting and heating. That is, a multilayer ceramic capacitor having excellent thermal shock resistance is obtained, and a multilayer ceramic capacitor having improved solder jointability to a printed wiring board or the like due to its bending strength is obtained.
【００１８】[0018]
【発明の実施の形態】以下、本発明の積層セラミックコ
ンデンサを図面に基づいて詳説する。図１は本発明の積
層セラミックコンデンサの外観斜視図であり、図２は図
１のＡ−Ａ線断面図であり、図３は、端子電極の構造を
示す断面図である。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, a multilayer ceramic capacitor according to the present invention will be described in detail with reference to the drawings. FIG. 1 is an external perspective view of the multilayer ceramic capacitor of the present invention, FIG. 2 is a cross-sectional view taken along line AA of FIG. 1, and FIG. 3 is a cross-sectional view showing a structure of a terminal electrode.
【００１９】本発明の積層セラミックコンデンサは、誘
電体磁器層１と内部電極層２とが交互に積層されたコン
デンサ本体１０と、該コンデンサ本体１０の一対の端部
に形成された端子電極３、３とから構成されている。The multilayer ceramic capacitor of the present invention has a capacitor body 10 in which dielectric ceramic layers 1 and internal electrode layers 2 are alternately stacked, and terminal electrodes 3 formed on a pair of ends of the capacitor body 10. And 3.
【００２０】誘電体磁器層１は、ＢａＴｉＯ3 を主成分
としたペロブスカイト型複合酸化物から構成されてい
る。The dielectric ceramic layer 1 is composed of a perovskite-type composite oxide containing BaTiO 3 as a main component.
【００２１】内部電極層２は、誘電体磁器層１間に配置
される。そして、誘電体磁器層１を介して厚み方向に隣
接しあう一方の内部電極層２は、コンデンサ本体１０の
一対の端部の一方に延出し、他方の内部電極層２は、コ
ンデンサ本体１０の一対の端部の他方に延出している。
このような内部電極層２は、Ｎｉなどの卑金属から構成
される。このようにＮｉなどの卑金属の内部電極層２に
よれば、ＡｇやＡｇ−Ｐｄの内部電極層２を有する積層
セラミックコンデンサに比較して安価となる。The internal electrode layers 2 are arranged between the dielectric ceramic layers 1. One internal electrode layer 2 adjacent in the thickness direction via the dielectric ceramic layer 1 extends to one of a pair of ends of the capacitor body 10, and the other internal electrode layer 2 It extends to the other of the pair of ends.
Such an internal electrode layer 2 is made of a base metal such as Ni. As described above, according to the internal electrode layer 2 of a base metal such as Ni, the cost is lower than that of the multilayer ceramic capacitor having the internal electrode layer 2 of Ag or Ag-Pd.
【００２２】誘電体磁器層１、内部電極層２が交互に積
層されたコンデンサ本体１０の一対の端部には端子電極
３が形成されている。この端子電極３は、例えば、コン
デンサ本体側からＮｉを含有する厚膜下地導体膜（以
下、外部端子という）４、Ｎｉメッキ層５、ハンダや錫
メッキ層６の順に積層された構造となっている。また、
外部端子４上に導電性樹脂層を設け、その表面にメッキ
処理を施しても構わない。Terminal electrodes 3 are formed at a pair of ends of the capacitor body 10 in which the dielectric ceramic layers 1 and the internal electrode layers 2 are alternately laminated. The terminal electrode 3 has, for example, a structure in which a thick base conductor film containing Ni (hereinafter, referred to as an external terminal) 4, a Ni plating layer 5, a solder or tin plating layer 6 are laminated in this order from the capacitor body side. I have. Also,
A conductive resin layer may be provided on the external terminals 4 and the surface thereof may be plated.
【００２３】本発明の積層セラミックコンデンサは以下
のようにして作製される。例えば、非還元性誘電体磁器
組成物からなる未焼成グリーンシート上に、例えばＮｉ
等の卑金属を主成分とする内部電極層用導電性ペースト
を用いて、内部電極層の形状に応じて印刷して未焼成導
体膜を形成し、このようなグリーンシートを複数積層し
た後、所定形状に切断し、脱バイ処理後、非還元性雰囲
気において一体的に焼成し、コンデンサ本体１０を作製
する。この後所望により、高酸素濃度の雰囲気で熱処理
する。The multilayer ceramic capacitor of the present invention is manufactured as follows. For example, on an unfired green sheet made of a non-reducing dielectric ceramic composition, for example, Ni
Using a conductive paste for an internal electrode layer containing a base metal such as a main component as a main component, printing is performed in accordance with the shape of the internal electrode layer to form an unfired conductive film. After being cut into a shape and a de-bubbling treatment, it is integrally fired in a non-reducing atmosphere to produce the capacitor body 10. Thereafter, if desired, heat treatment is performed in an atmosphere having a high oxygen concentration.
【００２４】次に、コンデンサ本体１０の両端部に、Ｎ
ｉ粉末、Ａｇ粉末、ガラスフリットを含む外部端子用導
電性ペーストを塗布し、低酸素濃度の雰囲気で焼き付け
外部端子４を形成する。そして、外部端子４をメッキ液
中に浸漬し、メッキ層５、６を形成することにより作製
される。Next, at both ends of the capacitor body 10, N
An external terminal conductive paste containing i powder, Ag powder, and glass frit is applied and baked in a low oxygen concentration atmosphere to form the external terminals 4. Then, the external terminals 4 are immersed in a plating solution to form the plating layers 5 and 6, thereby producing the external terminals 4.
【００２５】上述の内部電極層２となる導体膜は、Ｎｉ
などの卑金属粉末、例えばＳｉ−Ｂａ−Ｌｉ−Ｃａ系酸
化物を主成分とするガラスフリット、必要に応じて誘電
体材料の共材粉末などからなる導電性ペーストを用い
る。The conductor film serving as the internal electrode layer 2 is made of Ni
For example, a conductive paste made of a base metal powder such as a glass frit containing a Si-Ba-Li-Ca-based oxide as a main component and a co-material powder of a dielectric material is used as needed.
【００２６】また、端子電極３の下地導体膜である外部
端子４は、Ｎｉ系粉末と、Ａｇ粉末と、ガラスフリット
と、有機ビヒクルとからなる導電性ペーストを用いる。The external terminals 4 serving as a base conductor film of the terminal electrodes 3 use a conductive paste composed of Ni-based powder, Ag powder, glass frit, and an organic vehicle.
【００２７】ここで、外部端子用導電性ペーストのＮｉ
系粉末とは、Ｎｉ単体の粉末、Ｃｕ−Ｎｉ、Ｃｒ−Ｎｉ
などのＮｉ合金粉末などが例示できる。また、Ｎｉ系粉
末や銀粉末の平均粒径１〜７μｍのものが好適であり、
そして、Ｎｉ系粉末や銀粉末からなる金属成分外部端子
用導電性ペースト中の含有量は、全量中５０〜７５重量
％が望ましい。Here, the conductive paste for external terminals Ni
System powder refers to powder of Ni alone, Cu-Ni, Cr-Ni
And the like can be exemplified. Further, Ni-based powder or silver powder having an average particle diameter of 1 to 7 μm is preferable,
The content of the metal component external terminal conductive paste made of Ni-based powder or silver powder is desirably 50 to 75% by weight based on the total amount.
【００２８】ガラスフリットとしては、Ｂ2 Ｏ3 −Ｚｎ
Ｏ−ＳｉＯ2 −ＢａＯ系、Ｂ2 Ｏ3−ＺｎＯ−ＢａＯ−
Ａｌ2 Ｏ3 系等のガラスフリットが用いられるが、この
うちＢ2 Ｏ3 −ＺｎＯ−ＳｉＯ2 −ＢａＯ系ガラスフリ
ットが望ましい。その含有量は１０〜３０重量％が望ま
しい。ガラスフリットはＡｌ2 Ｏ3 、ＳｒＯ、ＣａＯを
含有しても良い。As the glass frit, B 2 O 3 —Zn
O-SiO 2 -BaO-based, B 2 O 3 -ZnO-BaO-
Glass frit al 2 O 3 system or the like is used, of which B 2 O 3 -ZnO-SiO 2 -BaO -based glass frit is preferable. Its content is preferably from 10 to 30% by weight. The glass frit may contain Al 2 O 3 , SrO, CaO.
【００２９】有機ビヒクルとしては、例えばイソブチル
メタクレート（ＩＢＭＡ）が用いられ、その含有量は１
０〜２０重量％が望ましい。As the organic vehicle, for example, isobutyl methacrylate (IBMA) is used.
0 to 20% by weight is desirable.
【００３０】上述のように、Ｎｉ系粉末に、Ａｇ粉末を
含有せしめたのは、外部端子用導電性ペーストを低酸素
濃度雰囲気（還元性雰囲気）で焼き付けする時に、８０
０℃以下の低温で端子電極の緻密性を向上させるためで
ある。As described above, the reason that the Ni-based powder is made to contain the Ag powder is that when the conductive paste for external terminals is baked in a low-oxygen-concentration atmosphere (reducing atmosphere), the Ag-containing powder is used.
This is for improving the denseness of the terminal electrode at a low temperature of 0 ° C. or lower.
【００３１】また、Ａｇ粉末を添加することにより、Ｎ
ｉ金属の焼結による応力を緩和させ，機械的性能（たわ
み試験）を向上することができる。Further, by adding Ag powder, N
The stress due to the sintering of the i-metal can be reduced, and the mechanical performance (deflection test) can be improved.
【００３２】また、Ｎｉ、Ａｇと低温では酸化されにく
い金属を使用しているため端子電極中のバインダーの脱
バインダーが十分にでき、焼成中に誘電体磁器層１を還
元させ信頼性を劣化させることはない。Further, since a metal which is hardly oxidized at a low temperature, such as Ni and Ag, is used, the binder in the terminal electrode can be sufficiently removed, and the dielectric ceramic layer 1 is reduced during firing, thereby deteriorating the reliability. Never.
【００３３】Ａｇ粉末の含有量は、内部電極層２の接合
性を向上するという点から、Ｎｉ系粉末及び銀粉末のか
らなる金属成分中、１０〜９０重量％含有することが望
ましい。The content of the Ag powder is preferably 10 to 90% by weight in the metal component composed of the Ni-based powder and the silver powder from the viewpoint of improving the bonding property of the internal electrode layer 2.
【００３４】このように調整された外部端子用導電性ペ
ーストによって形成された外部端子４は、図４に示すよ
うに、Ｎｉ相８（図中黒塗り部分）に、Ａｇ相９（図中
白抜き部分）及びガラス相７（図中白抜き斜線部分）部
分）が均一に分散する。そして、Ａｇ相９が外部端子４
中に１０〜９０体積％存在するものである。As shown in FIG. 4, the external terminals 4 formed of the external terminal conductive paste thus adjusted are connected to the Ni phase 8 (black portion in the drawing) and the Ag phase 9 (white in the drawing). (A blank portion) and a glass phase 7 (a hatched portion in the figure) are uniformly dispersed. The Ag phase 9 is connected to the external terminal 4
10 to 90% by volume.
【００３５】Ａｇ相を外部端子４中に１０〜９０体積％
としたのは、１０体積％よりも少ない場合には、外部端
子４の緻密性が低く、その表面にメッキする場合には内
部まで浸透し、耐熱衝撃によりコンデンサ本体１０にク
ラックなどが発生してしまい、信頼性不良となるためで
ある。また、Ｎｉ金属の応力により機械的強度が弱くな
る。10 to 90% by volume of Ag phase in external terminal 4
The reason is that when less than 10% by volume, the denseness of the external terminal 4 is low, and when plating on the surface, the external terminal 4 penetrates to the inside and cracks and the like occur in the capacitor body 10 due to heat shock. This is because the reliability becomes poor. In addition, the mechanical strength is weakened by the stress of the Ni metal.
【００３６】一方、９０体積％よりも多くなると、Ｎｉ
相８が相対的に低下して、内部電極層２との接続による
導電性が低下し、端子電極としての機能が低下してしま
い、その結果、積層セラミックコンデンサの静電容量が
急激に低下する。On the other hand, if it exceeds 90% by volume, Ni
The phase 8 relatively decreases, the conductivity due to connection with the internal electrode layer 2 decreases, and the function as a terminal electrode decreases, and as a result, the capacitance of the multilayer ceramic capacitor rapidly decreases. .
【００３７】以上のことから、Ａｇ相９は、外部端子４
中に１０〜９０体積％であることが望ましい。From the above, the Ag phase 9 is connected to the external terminal 4
It is desirable that the content is 10 to 90% by volume.
【００３８】そして、上述したように、ＮｉとＡｇとが
強固に接触しており、Ａｇが他の金属と激しく合金を形
成しないため、外部端子４の厚みを４０μｍ以下にして
も、コンデンサ本体１０の端部を露出させることがな
く、導電率を低下させることもないため、安定した静電
容量を容易に得ることができる。As described above, Ni and Ag are in strong contact with each other, and Ag does not violently form an alloy with other metals. Therefore, even if the thickness of the external terminal 4 is set to 40 μm or less, the capacitor body 10 Since the end portions are not exposed and the conductivity is not reduced, a stable capacitance can be easily obtained.
【００３９】上述のように、外部端子用導電性ペースト
を低酸素濃度雰囲気（還元性雰囲気）で焼き付けする、
誘電体磁器層１は還元されることがなく、誘電体磁器層
１の絶縁抵抗が低下することがない。As described above, the conductive paste for external terminals is baked in a low oxygen concentration atmosphere (reducing atmosphere).
The dielectric ceramic layer 1 is not reduced, and the insulation resistance of the dielectric ceramic layer 1 does not decrease.
【００４０】なお、内部電極層２の卑金属材料として、
Ｎｉ系金属を用いることにより、Ｎｉ金属主成分とする
外部端子４との接合部分を、ＮｉとＮｉで行なうことが
できるため、内部電極層２と外部端子４とが一体化し、
機械的な接合及び電気的な接続を安定化を図ることがで
きる。The base metal material of the internal electrode layer 2 is
By using a Ni-based metal, the joint between the external terminal 4 mainly composed of the Ni metal and the external terminal 4 can be made of Ni and Ni. Therefore, the internal electrode layer 2 and the external terminal 4 are integrated,
Mechanical joining and electrical connection can be stabilized.
【００４１】さらに、本発明によれば、Ｎｉを主成分と
する内部電極層２と誘電体磁器層１とが交互に積層した
焼成前のグリーンシート積層体を、内部電極層２が酸化
されない程度の低い酸素分圧中で焼成処理し、その後、
誘電体磁器層１の絶縁抵抗値の回復のために、高い酸素
濃度雰囲気で熱処理し、Ｎｉを主成分とする端子用導電
性ペーストをコンデンサ本体１０の端面に形成し、酸化
されない程度の酸素分圧で焼き付けても、内部電極層２
と外部端子４との接合信頼性は高く、外部端子４のＮｉ
相８の相間にガラス相７が充填しているために緻密性が
高く、メッキによる影響を受けにくい。しかも内部電極
層２にＮｉを用いた低コストの積層セラミックコンデン
サを得ることができる。Further, according to the present invention, the green sheet laminate before firing in which the internal electrode layers 2 mainly composed of Ni and the dielectric porcelain layers 1 are alternately laminated is prepared so that the internal electrode layers 2 are not oxidized. Baking in a low oxygen partial pressure of
In order to recover the insulation resistance value of the dielectric ceramic layer 1, heat treatment is performed in a high oxygen concentration atmosphere to form a terminal conductive paste mainly composed of Ni on the end face of the capacitor body 10. Internal electrode layer 2
And the external terminal 4 has high bonding reliability.
Since the glass phase 7 is filled between the phases 8, the denseness is high and the glass phase 7 is hardly affected by plating. Moreover, a low-cost multilayer ceramic capacitor using Ni for the internal electrode layer 2 can be obtained.
【００４２】[0042]
【実施例】チタン酸バリウム（ＢａＴｉＯ3 ）とチタン
酸バリウム１００重量部に対して酸化イットリウム（Ｙ
2 Ｏ3 ）を１重量部、酸化マグネシウム（ＭｇＯ）を
０．２重量部、炭酸マンガン（ＭｎＣＯ3 ）０．１重量
部、Ｌｉ−Ｓｉ（５０／５０）を０．５重量部含有する
誘電体磁器組成物に、有機系粘結剤と媒体からなるバイ
ンダーを添加、攪拌してセラミックスラリーを調整した
後、得られたセラミックスラリーを脱泡し、ドクターブ
レード法により厚さ７μｍの誘電体磁器層１となるセラ
ミックグリーンシートを成形した。EXAMPLE Barium titanate (BaTiO 3 ) and 100 parts by weight of barium titanate were mixed with yttrium oxide (Y).
Dielectric containing 1 part by weight of 2 O 3 ), 0.2 part by weight of magnesium oxide (MgO), 0.1 part by weight of manganese carbonate (MnCO 3 ), and 0.5 part by weight of Li-Si (50/50). After adding a binder composed of an organic binder and a medium to the body porcelain composition and stirring to adjust the ceramic slurry, the obtained ceramic slurry is defoamed, and a 7 μm-thick dielectric ceramic is obtained by a doctor blade method. A ceramic green sheet to be the layer 1 was formed.
【００４３】得られたグリーンシート上にＮｉ粉末を含
む内部電極層用ペーストを用いて内部電極層２となる導
体膜を所定形状にスクリーン印刷する。A conductive film to be the internal electrode layer 2 is screen-printed on the obtained green sheet into a predetermined shape using an internal electrode layer paste containing Ni powder.
【００４４】その後、上述の誘電体磁器組成物と同一の
セラミックペーストを内部電極層パターン上に塗布し、
さらに上述の内部電極層用ペーストを塗布し、これらの
工程をそれぞれ１５０回繰り返して積層体を作製し、所
定寸法（２１２５型）に切断してグリーンチップ（焼成
前の積層成形体）を作製した。Thereafter, the same ceramic paste as the above-mentioned dielectric ceramic composition is applied on the internal electrode layer pattern,
Further, the above-mentioned paste for an internal electrode layer was applied, and these steps were repeated 150 times, respectively, to produce a laminate, which was cut into a predetermined size (2125 type) to produce a green chip (a laminate molded body before firing). .
【００４５】その積層成形体を大気中で４００℃にて脱
バインダーを行い、その後１２５０℃（ＰＯ2 １０-11
ａｔｍ）で２時間焼成し、続いて大気中８００℃で再酸
化処理をした。The laminate was debindered at 400 ° C. in the air, and then 1250 ° C. (PO 2 10 −11).
atm) for 2 hours, followed by reoxidation at 800 ° C. in the atmosphere.
【００４６】次に、Ｎｉ粉末、Ａｇ粉末、ガラスフリッ
ト、有機ビヒクルを用いて端子用導電性ペーストを作製
した。Ｎｉ粉末としては平均粒径３μｍのものを使用し
た。Next, a conductive paste for terminals was prepared using Ni powder, Ag powder, glass frit, and organic vehicle. Ni powder having an average particle diameter of 3 μm was used.
【００４７】またガラスフリットは、４０モル％のＢ2
Ｏ3 と、２０モル％のＺｎＯと、７モル％のＳｉＯ
2 と、２０モル％のＢａＯと、６モル％のＡｌ2 Ｏ
3 と、７モル％のＣａＯからなるものを用いた。The glass frit contains 40 mol% of B 2
O 3 , 20 mol% ZnO and 7 mol% SiO
2 , 20 mol% BaO and 6 mol% Al 2 O
3 and 7 mol% of CaO were used.
【００４８】有機ビヒクルとしてはイソブチルメタクレ
ートを用いた。これらのＮｉ粉末、Ａｇ粉末、ガラスフ
リット、有機ビヒクルを表１に示す割合にて３本ロール
で混合し、本発明の端子用導電性ペーストを作製した。As an organic vehicle, isobutyl methacrylate was used. These Ni powder, Ag powder, glass frit, and organic vehicle were mixed at the ratio shown in Table 1 with three rolls to prepare the conductive paste for terminals of the present invention.
【００４９】この後、端子用導電性ペーストをロール転
写法により焼き上げで２０〜４０μｍの厚みになるよう
コンデンサ本体の端面に塗布し、７００℃にてＮ2 中に
て焼き付けを行い、外部端子を形成し、次にこの外部端
子の表面に、Ｎｉメッキ、Ｓｎメッキを施した。Thereafter, a conductive paste for a terminal is applied to the end surface of the capacitor body by baking by a roll transfer method so as to have a thickness of 20 to 40 μm, and baked in N 2 at 700 ° C. Then, Ni plating and Sn plating were applied to the surfaces of the external terminals.
【００５０】外部端子中のＡｇ相の存在量を、焼成した
試料の外部端子を研磨し、電子走査顕微鏡（ＳＥＭ）観
察を行い、面積比で求めた。また、試料の静電容量、誘
電損失を測定した。The abundance of the Ag phase in the external terminal was determined by polishing the external terminal of the fired sample and observing it with an electron scanning microscope (SEM) to determine the area ratio. In addition, the capacitance and dielectric loss of the sample were measured.
【００５１】また、１５０℃、４０Ｖで高温負荷試験を
行い、４０時間以内に発生するショート不良率（絶縁抵
抗１ＭΩ以下）を調べ、信頼性を調べた。Further, a high-temperature load test was performed at 150 ° C. and 40 V, and a short-circuit defect rate (insulation resistance of 1 MΩ or less) occurring within 40 hours was examined, and reliability was examined.
【００５２】耐熱衝撃性を見るために、２５０℃の半田
槽の中に作製した試料１００ケを浸漬し、外観でコンデ
ンサ本体１０のクラックの発生率を観察した。In order to check the thermal shock resistance, 100 samples prepared were immersed in a solder bath at 250 ° C., and the appearance of cracks in the capacitor body 10 was visually observed.
【００５３】内部電極層２の腐食を見るために温度８５
℃、湿度８５％において直流電圧１０Ｖを印加して高湿
負荷試験を行い、１２５時間以内に発生する絶縁不良数
（絶縁抵抗１ＧΩ以下）を調べた。In order to observe the corrosion of the internal electrode layer 2, the temperature was set to 85
A high-humidity load test was performed by applying a DC voltage of 10 V at 85 ° C. and a humidity of 85%, and the number of insulation defects (insulation resistance of 1 GΩ or less) occurring within 125 hours was examined.
【００５４】機械的強度を見るためにガラスエポキシ基
板（ｔ＝１．６ｍｍ）を用いて曲げ強度試験を行った。
なお、良品の判定とし、静電容量が７００ｎＦ以上、誘
電損失が３．０％以下、不良、クラックが一切発生しな
いもの、さらにたわみ量をが２．０ｍｍ以上とした。こ
れらの結果を表２に記載した。In order to check the mechanical strength, a bending strength test was performed using a glass epoxy substrate (t = 1.6 mm).
A non-defective product was determined to have a capacitance of 700 nF or more, a dielectric loss of 3.0% or less, a defect and no crack, and a deflection of 2.0 mm or more. These results are shown in Table 2.
【００５５】[0055]
【表１】 [Table 1]
【００５６】[0056]
【表２】 [Table 2]
【００５７】これらの表１および表２から、Ａｇ粉末を
添加しない（試料番号１）及び銀粉末が１０重量％未満
（試料番号２）では、Ａｇ相の体積比率が１０体積％未
満となり、静電容量は高いものの、耐熱衝撃性、湿中負
荷試験での不良率も大きいことが判る。また、機械的強
度が弱いことが分かる。また端子電極を４０μｍ以下と
した場合容量のばらつきが大きくなる。From Tables 1 and 2, it can be seen that when the Ag powder was not added (Sample No. 1) and the silver powder was less than 10% by weight (Sample No. 2), the volume ratio of the Ag phase was less than 10% by volume, It can be seen that although the electric capacity is high, the thermal shock resistance and the defective rate in the humidity and medium load test are also large. Also, it can be seen that the mechanical strength is weak. Further, when the terminal electrode is set to 40 μm or less, variation in capacitance becomes large.
【００５８】これに対して、Ａｇ粉末が９０重量％を越
える（試料番号１０、１１）では、Ａｇ相の体積比率が
９０体積％を越えると静電容量の急激な低下が確認され
る。On the other hand, when the Ag powder exceeds 90% by weight (Sample Nos. 10 and 11), when the volume ratio of the Ag phase exceeds 90% by volume, a sharp decrease in capacitance is confirmed.
【００５９】尚、上述の実施例では、Ｎｉ系粉末とＡｇ
粉末とを用いて金属成分を形成しているが、さらに、Ｐ
ｄ粉末を添加することもできる。このＰｄ粉末は、Ａｇ
粉末と焼成しても、大きく体積減少しないことから適用
できるものであり、また焼結性も十分に考慮する必要が
ある。In the above embodiment, the Ni powder and the Ag powder were used.
The metal component is formed using powder and
d powder can also be added. This Pd powder is Ag
Even if it is fired with a powder, it can be applied because the volume does not greatly decrease, and sinterability must be sufficiently considered.
【００６０】[0060]
【発明の効果】以上詳述したとおり、本発明の積層セラ
ミックコンデンサでは、Ｎｉ粒子に、Ａｇ粉末、を添加
した外部端子用導電性ペーストを用いて外部端子を形成
しため、緻密性を向上でき、外部端子表面をハンダ濡れ
性を向上するためのメッキ処理時に、メッキ液が外部端
子に浸入することがないので、内部電極層にも浸入せ
ず、積層セラミックコンデンサをハンダにより基板等に
固着する際の加熱によっても、コンデンサ本体に割れ等
が生じることがなく、耐熱衝撃性に優れ、機械的強度の
優れた積層セラミックコンデンサを得ることができる。As described in detail above, in the multilayer ceramic capacitor of the present invention, since the external terminals are formed using the conductive paste for external terminals obtained by adding Ag powder to Ni particles, the denseness can be improved. During the plating process for improving the solder wettability of the external terminal surface, the plating solution does not enter the external terminals, so that the plating solution does not enter the internal electrode layers, and the multilayer ceramic capacitor is fixed to a substrate or the like by soldering. Even when heating is performed, a multilayer ceramic capacitor having excellent thermal shock resistance and excellent mechanical strength can be obtained without causing a crack or the like in the capacitor body.
【図１】本発明の積層セラミックコンデンサの外観斜視
図である。FIG. 1 is an external perspective view of a multilayer ceramic capacitor according to the present invention.
【図２】図１中のＡ−Ａ線断面図である。FIG. 2 is a sectional view taken along line AA in FIG.
【図３】端子電極の近傍を示す拡大断面図である。FIG. 3 is an enlarged sectional view showing the vicinity of a terminal electrode.
【図４】外部端子を拡大して示す断面図である。FIG. 4 is an enlarged sectional view showing an external terminal.
【図５】従来の積層セラミックコンデンサの外部端子近
傍を示す断面図である。FIG. 5 is a cross-sectional view showing the vicinity of an external terminal of a conventional multilayer ceramic capacitor.
１・・・誘電体磁器層 ２・・・内部電極層 １０・・・コンデンサ本体 ３・・・端子電極 ４・・・外部端子 ５・・・Ｎｉメッキ膜 ６・・・ＳｎまたはＳｎ−Ｐｂメッキ膜 ７・・・ガラス相 ８・・・Ｎｉ相 ９・・・Ａｇ相 DESCRIPTION OF SYMBOLS 1 ... Dielectric ceramic layer 2 ... Internal electrode layer 10 ... Capacitor main body 3 ... Terminal electrode 4 ... External terminal 5 ... Ni plating film 6 ... Sn or Sn-Pb plating Film 7 ・ ・ ・ Glass phase 8 ・ ・ ・ Ni phase 9 ・ ・ ・ Ag phase
Claims (1)
層を交互に積層してなるコンデンサ本体の両端部に、１
０〜９０体積％のＡｇ相と、Ｎｉ及びＮｉ合金相とか成
る外部端子を具備した積層セラミックコンデンサ。1. A capacitor body comprising alternately laminated internal electrode layers made of a base metal and dielectric ceramic layers,
A multilayer ceramic capacitor having external terminals composed of 0 to 90% by volume of an Ag phase and Ni and a Ni alloy phase.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP05025099A JP3744710B2 (en) | 1999-02-26 | 1999-02-26 | Multilayer ceramic capacitor |
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| JP05025099A JP3744710B2 (en) | 1999-02-26 | 1999-02-26 | Multilayer ceramic capacitor |
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| JP3744710B2 JP3744710B2 (en) | 2006-02-15 |
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| JP05025099A Expired - Fee Related JP3744710B2 (en) | 1999-02-26 | 1999-02-26 | Multilayer ceramic capacitor |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007234893A (en) * | 2006-03-01 | 2007-09-13 | Tdk Corp | Coil part |
| WO2013128957A1 (en) * | 2012-02-29 | 2013-09-06 | 株式会社村田製作所 | Conductive paste, electronic component, and method for producing electronic component |
| JP2015187977A (en) * | 2014-03-13 | 2015-10-29 | 三ツ星ベルト株式会社 | Conductive laminate and method for manufacturing the same |
| JP2019179874A (en) * | 2018-03-30 | 2019-10-17 | Ｊｘ金属株式会社 | External electrode of ceramic laminate |
-
1999
- 1999-02-26 JP JP05025099A patent/JP3744710B2/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007234893A (en) * | 2006-03-01 | 2007-09-13 | Tdk Corp | Coil part |
| WO2013128957A1 (en) * | 2012-02-29 | 2013-09-06 | 株式会社村田製作所 | Conductive paste, electronic component, and method for producing electronic component |
| JPWO2013128957A1 (en) * | 2012-02-29 | 2015-07-30 | 株式会社村田製作所 | Conductive paste, electronic component, and method of manufacturing electronic component |
| US9653211B2 (en) | 2012-02-29 | 2017-05-16 | Murata Manufacturing Co., Ltd. | Conductive paste, electronic component and method for manufacturing electronic component |
| US10090108B2 (en) | 2012-02-29 | 2018-10-02 | Murata Manufacturing Co., Ltd. | Conductive paste, electronic component, and method for manufacturing electronic component |
| JP2015187977A (en) * | 2014-03-13 | 2015-10-29 | 三ツ星ベルト株式会社 | Conductive laminate and method for manufacturing the same |
| JP2019179874A (en) * | 2018-03-30 | 2019-10-17 | Ｊｘ金属株式会社 | External electrode of ceramic laminate |
| JP7046679B2 (en) | 2018-03-30 | 2022-04-04 | Ｊｘ金属株式会社 | External electrodes of ceramic laminate |
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| Publication number | Publication date |
|---|---|
| JP3744710B2 (en) | 2006-02-15 |
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