JP4496639B2 - Electronic component and manufacturing method thereof - Google Patents

Description

【００９２】
表１に示す結果から、第２導電層中のガラスとＲｕＯ_２ との重量比を調整することで、ＥＳＲの制御が可能であることが確認できた。また、メッキ前後のＥＳＲの変動も少ないことが確認できた。
【００９３】
また、本実施例の試料を、レギュレータＩＣの平滑用コンデンサとして用い、１００ｋＨｚで動作させたところ、発振等の電圧変動を生じることなく正常に動作した。
【００９４】
また、本実施例の試料について、コンデンサの加速試験である高温負荷試験（８５℃、定格の２倍の電圧印加）および耐湿負荷試験（８５℃、８５％、定格電圧印加）を行ったところ、ＥＳＲの変動およびその他の電気特性に変化は認められなかった。
【００９５】
実施例２
第２導電層用ペーストの塗布および乾燥後に直ちに焼き付けを行うことなく、第３導電層用ペーストの塗布および乾燥後に、空気中で同時に焼き付け処理を行った以外は、実施例１と同様にしてコンデンサ試料を作製し、同様な試験を行った。結果を表２に示す。
【００９６】
【表２】

【００９７】
表２に示すように、実施例１に比較して、メッキ前後のＥＳＲ変動個数がさらに少なくなり、ＥＳＲの制御特性がおよび安定性がさらに増大することが確認できた。
【００９８】
比較例１
図１に示す第３導電層２４を形成しない以外は、前記実施例１と同様にしてコンデンサ試料を作製しようとしたが、第２導電層２２が酸化物で構成されるために、その外面にメッキ層２６を形成することができなかった。なお、無電解メッキを用いることにより、メッキ層を形成することは可能ではあるが、抵抗のばらつきが大きくなってしまい、実用的でない。
比較例２
図１に示す第１導電層２０を形成しない以外は、前記実施例１と同様にしてコンデンサ試料を作製し、同様な試験を行った。
【００９９】
コンデンサ素体１０に対して、第１導電層２０を形成しないで、直接に第２導電層２２を形成しようとしたので、内部電極であるＮｉと電気的な接続が確保できなくなり設計通りの静電容量およびその他の電気特性を得ることができなかった。
【０１００】
実施例３
第２導電層中のガラス組成として、ストロンチウム系ガラスを用いた以外は、実施例１と同様にしてコンデンサ試料を作製し、同様な試験を行った場合も、同様な傾向が認められた。
【０１０１】
実施例４
第２導電層中の導電材として、Ｂｉ_２ Ｒｕ_２ Ｏ_７ を用いた以外は、実施例１と同様にしてコンデンサ試料を作製し、同様な試験を行った場合も、同様な傾向が認められた。
しかも、本実施例のコンデンサ試料について、耐湿負荷試験（８５℃／８５％ＲＨ： 定格電圧印加）を１０００時間行い、その前後におけるＥＳＲの変動率を測定したところ、±０．５％以内であり、安定したＥＳＲが得られることが確認できた。なお、第２導電層中の導電材としてＲｕＯ_２ を用いた実施例１のコンデンサ試料についても、同様な耐湿負荷試験を行ったところ、ＥＳＲの変動率は±３％であった。
【０１０２】
実施例５
第１導電層および第３導電層のガラスとして、亜鉛系マンガン含有ガラス（ＺｎＯ：６０重量％，Ｂ_２ Ｏ_３ ：２０重量％，ＳｉＯ_２ ：１０重量％，ＭｎＯ：１０重量％）を用いた以外は、実施例１と同様にしてコンデンサ試料を作製し、同様な試験を行った結果を、表３に示す。
【０１０３】
【表３】

【０１０４】
表３に示すように、亜鉛系マンガン含有ガラスを用いることで、実施例１に比較して、メッキ前後のＥＳＲ変動個数がさらに少なくなり、ＥＳＲの制御特性がおよび安定性がさらに増大することが確認できた。
【０１０５】
実施例６
第２導電層中の導電性物質として、グラファイト・カーボン（平均粒径：１．１μｍ）を用いた以外は、実施例１と同様にしてコンデンサ試料を作製し、同様な試験を行った結果を、表４に示す。
【０１０６】
【表４】

【０１０７】
実施例７
第１導電層の導電材料として、ＡｇとＰｄとの組成比が３０：７０であるＡｇ−Ｐｄ（平均粒径：０.８μｍ）の合金粉末を用いた以外は、実施例１と同様にしてコンデンサ試料を作製し、同様な試験を行った場合も、同様な傾向が認められた。
しかも、本実施例７のコンデンサ試料では、ＥＳＲのばらつき（ＣＶ値）が５．５％であり、ＣＶ値が１３％であった実施例１（ＡｇとＰｄとの混合粉末）に比較して、さらに小さくできることが確認できた。なお、実施例１および実施例７において、ＥＳＲのＣＶ値は、第２導電層中のガラスとＲｕＯ_２ との重量比を、３.０とした場合において、メッキ前の試料を５０個準備し、それらのＥＳＲを測定し、そのばらつきを求めることにより測定した。
【０１０８】
【発明の効果】
以上説明してきたように、本発明によれば、積層セラミックコンデンサなどの電子部品の外部端子電極部に抵抗機能を付与し、メッキ処理による抵抗の変動がなく、抵抗の経時変化のない極めて高い信頼性を持つ電子部品、より具体的にはＣＲ複合電子部品を実現することができる。
【図面の簡単な説明】
【図１】 図１は本発明の一実施形態に係る電子部品としての積層セラミックコンデンサの要部断面図である。
【符号の説明】
２… 積層セラミックコンデンサ
４… 誘電体層
６，８… 内部電極層
１０… 素子本体
１２，１４… 外部電極端子
２０… 第１導電層
２２… 第２導電層
２４… 第３導電層
２６… メッキ層[0001]
BACKGROUND OF THE INVENTION
The present invention is an electronic component such as a monolithic ceramic capacitor that has little resistance variation even by plating on the terminal electrode, can accurately control the equivalent series resistance (ESR), has little resistance change with time, and has high reliability. And a manufacturing method thereof.
[0002]
[Prior art]
With the development of information communication, electronic devices are becoming increasingly smaller, especially in the mobile phone market. These cellular phones incorporate a regulator IC, to which a multilayer ceramic capacitor is connected so as to form an output smoothing circuit.
[0003]
However, the multilayer ceramic capacitor has a very low equivalent series resistance (ESR), and a signal in the circuit loops to cause an oscillation phenomenon. As a result, it tends to be a noise during conversation. That is, in the secondary side circuit of the regulator IC, the ESR of the smoothing circuit greatly affects the phase characteristics of the feedback loop, and a problem arises particularly when the ESR becomes extremely low. That is, when a multilayer ceramic capacitor having a low ESR is used as the smoothing capacitor, the secondary side smoothing circuit is equivalently composed of only the L and C components, and the phase components existing in the circuit are ± 90 ° and 0 It becomes only °, and it oscillates easily with no phase margin.
[0004]
In order to suppress this oscillation, a capacitor with a large ESR is required. As a capacitor having a large ESR, there is an electrolytic capacitor using tantalum or aluminum, but it cannot be used in a mobile phone because of a critical problem in terms of reliability such as liquid leakage. For this reason, the current situation is that the noise at the time of using the mobile phone due to the capacitor for the smoothing circuit is left unattended.
[0005]
In order to solve such a problem, an electronic component having an increased ESR of a multilayer ceramic capacitor has been proposed. For example, in Japanese Patent No. 2578264, a metal oxide film is formed on the surface of an external terminal electrode of a multilayer ceramic capacitor, and this is used as a resistor to increase ESR, and the resistance value is controlled by the oxide film thickness. It is said.
[0006]
However, when actually manufacturing the capacitor disclosed in the patent, it is difficult to control the oxidation of the terminal electrode, and if the degree of oxidation is as large as possible, the internal electrode is also oxidized, and it can function as a capacitor. There is a problem that it becomes impossible. Even if only the terminal electrode can be oxidized, there is a problem because the terminal electrode is oxidized.
[0007]
That is, since the terminal electrode is oxidized, when plating the surface of the terminal electrode, it is necessary to form a plating film by electroless plating, and even the ceramic body is not plated during the plating. It is necessary to coat with resin or the like. For this reason, not only the process becomes complicated, but also the adhesion between the oxide film and the plating film (Ni film) is remarkably lowered, and peeling occurs between them, which is necessary and sufficient mechanical as an electronic component. There is a disadvantage that strength cannot be obtained. That is, when a lead wire is provided on the nickel plating film of the terminal electrode, the lead wire is easily peeled off.
[0008]
Also, for example, as described in Japanese Patent Application Laid-Open No. 59-225509, there is also known a laminate in which a resistor paste such as ruthenium oxide is laminated on a multilayer ceramic capacitor, and this is simultaneously fired to form a resistor. ing. However, when the terminal electrode is provided as it is, the equivalent circuit becomes a C / R or (LC / R) parallel circuit, and a series circuit cannot be obtained. Further, in order to obtain a series circuit, the shape of the terminal electrode becomes complicated, and the manufacturing process becomes complicated.
Further, in the above conventional capacitor structure, it is very difficult to control ESR, and a desired resistance value cannot be easily obtained.
[0009]
Recently, since various devices including a power source, or electric devices and electronic devices are used in various environments, the capacitor is required to have no change in characteristics even under severe use conditions. In particular, it is important that the ESR is stable over time.
[0010]
[Problems to be solved by the invention]
The object of the present invention is to provide a highly reliable multilayer ceramic capacitor that is less susceptible to resistance fluctuations even by plating on the terminal electrode portion, can accurately control the equivalent series resistance (ESR), has little resistance change with time, and the like. It is providing the electronic component and its manufacturing method.
[0011]
[Means for Solving the Problems]
In order to achieve the above object, an electronic component according to the present invention includes:
An element body in which dielectric layers and internal electrode layers are alternately laminated;
An electronic component having an external terminal electrode formed on the outer surface of the element body,
The external terminal electrode is
A first conductive layer formed directly on the outer surface of the element body so as to be electrically connected to at least a part of the internal electrode, and made of a hardly oxidizable material;
A second conductive layer formed on an outer surface of the first conductive layer and mainly including a mixture of a conductive material and an insulating material;
A third conductive layer formed on the outer surface of the second conductive layer and made of a hardly oxidizable material.
[0012]
The first conductive layer and the third conductive layer preferably include one or more metals selected from Pd, Ag, Pt, Au, Rh, Ir, and Ru. More preferably, the first conductive layer and the third conductive layer preferably contain these two or more kinds of alloys. Particularly preferably, the first conductive layer preferably contains an alloy of Ag and Pd.
[0013]
The conductive material is not particularly limited, and for example, a conductive oxide such as a metal oxide or a metal is used. The conductive oxide preferably contains at least one oxide selected from ruthenium oxide, ruthenium oxide compounds and graphite. Although it does not specifically limit as said insulating substance, For example, an insulating oxide is illustrated and it is preferable that glass and a metal oxide are included especially.
[0014]
It is preferable that the second conductive layer functions as a resistor that resists higher resistance than the first conductive layer and the third conductive layer.
[0015]
The average particle diameter of the particles forming the first conductive layer and the third conductive layer is preferably 0.1 to 30 μm.
[0016]
It is preferable that the average particle size of the conductive material particles forming the second conductive layer is 0.01 to 10 μm, and the average particle size of the insulating material particles is 0.01 to 10 μm.
[0017]
It is preferable that the first conductive layer and the third conductive layer contain glass. In this case, it is preferable that the glass of the said 1st conductive layer and the 3rd conductive layer contains manganese oxide. Moreover, it is more preferable that the content of manganese oxide in the glass containing manganese oxide is 0 to 40% by weight (not including 0%) with 100% by weight of the entire glass. Furthermore, it is preferable that the average particle diameter of the glass particles is 0.01 to 30 μm.
[0018]
A plating layer is preferably formed on the outer surface of the third conductive layer.
The internal electrode layer is not particularly limited, but preferably contains a base metal such as Ni.
[0019]
In order to achieve the above object, a method of manufacturing an electronic component according to the first aspect of the present invention includes:
Forming a device body in which dielectric layers and internal electrode layers are alternately laminated;
Applying and baking a first conductive layer paste containing a hardly oxidizable material on the outer surface of the element body to form a first conductive layer;
Applying and baking a second conductive layer paste mainly containing a mixture of a conductive material and an insulating material on the outer surface of the first conductive layer to form a second conductive layer;
Applying a third conductive layer paste containing a hardly oxidizable material to the outer surface of the second conductive layer and baking it to form a third conductive layer.
An electronic component manufacturing method according to a second aspect of the present invention includes:
Forming a device body in which dielectric layers and internal electrode layers are alternately laminated;
Applying and baking a first conductive layer paste containing a hardly oxidizable material on the outer surface of the element body to form a first conductive layer;
Applying a second conductive layer paste mainly containing a mixture of a conductive material and an insulating material to the outer surface of the first conductive layer;
Applying a third conductive layer paste containing a hardly oxidizable material to the outer surface of the second conductive layer paste, followed by baking to form a second conductive layer and a third conductive layer. .
[0020]
The first conductive layer paste is baked in an atmosphere (neutral or reducing atmosphere) that is not an oxidizing atmosphere, and the second conductive layer paste and the third conductive layer paste are baked in an oxidizing atmosphere. It is preferable to carry out with.
[0021]
The electronic component according to the present invention is not limited to a multilayer ceramic capacitor, and also includes a composite electronic component such as a CR composite electronic component having a capacitor element portion and an inductor element portion. In the CR composite electronic component, the element body is composed of a capacitor element portion and an inductor element portion, and the common external electrode terminal of these element portions is the external terminal structure in the present invention.
[0022]
[Action]
In the present invention, a resistance function is provided to a terminal electrode in an electronic component such as a multilayer ceramic capacitor, thereby enabling adjustment of ESR. In addition, in the present invention, a resistor composed of the second conductive layer containing ruthenium oxide or the like as a conductive material is formed between the hardly oxidizable (substantially not oxidized) first conductive layer and the third conductive layer. As a result, the resistance variation is small even by the plating process on the terminal electrode portion, the equivalent series resistance (ESR) can be accurately controlled, and a highly reliable electronic component with little change in resistance with time can be realized. .
[0023]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described based on embodiments shown in the drawings.
FIG. 1 is a cross-sectional view of a main part of a multilayer ceramic capacitor as an electronic component according to an embodiment of the present invention.
[0024]
As shown in FIG. 1, a multilayer ceramic capacitor 2 according to an embodiment of the present invention includes a capacitor element body 10 having a configuration in which dielectric layers 4 and internal electrode layers 6 and 8 are alternately stacked. At both ends in the X direction of the capacitor element body 10, a pair of external terminal electrodes 12 and 14 are formed which are electrically connected to the internal electrode layers 6 and 8 that are alternately arranged inside the element body 10. The shape of the capacitor element body 10 is not particularly limited, but is usually a rectangular parallelepiped shape. Also, there is no particular limitation on the dimensions, and it may be an appropriate dimension according to the application. Usually, (0.6 to 5.6 mm) × (0.3 to 5.0 mm) × (0.3 ˜1.9 mm).
[0025]
In the external terminal electrodes 12 and 14, the first conductive layer 20, the second conductive layer 22, and the third conductive layer 24 are stacked in order from the side electrically connected to the end of the internal electrode layer 6 or 8, respectively. A plated layer 26 is formed on the outer surface of the third conductive layer 24.
[0026]
The first conductive layer 20 is made of a hardly oxidizable metal (including an alloy). As the preferred hardly oxidizable metal, for example, at least one metal of Pd, Ag, Au, Pt, Rh, Ru, Ir, an alloy of Ag and Pd, or another alloy is preferable. . Particularly preferably, the first conductive layer 20 includes an alloy of Ag and Pd. By using an alloy, the metal component (Ag or Pd or the like) is less likely to diffuse into the insulating oxide (resistor glass component) in the second conductive layer 22, and the variation in ESR can be further reduced. .
[0027]
The second conductive layer 22 is made of a material containing a conductive oxide and an insulating oxide. The conductive oxide is not particularly limited as long as it is an oxide exhibiting conductivity, but preferably includes at least one selected from ruthenium oxide, a ruthenium oxide compound, and graphite. Examples of the ruthenium oxide compound include Bi.₂Ru₂O₇, SrRuO₃, CaRuO₃, Pb₂Ru₂O₆, BaRuO₃However, it is not limited to these. However, among these, Bi₂Ru₂O₇Is particularly preferred. Bi₂Ru₂O₇By selecting, stable ESR can be obtained even after the moisture resistance load test.
The graphite is preferably graphite / carbon.
[0028]
Further, the insulating oxide is not particularly limited, but it is preferable to select glass from the viewpoint of controlling the resistance value and securing the sinterability of the conductive material and the adhesiveness with the first conductive layer 20. . The composition of the glass is not particularly limited, but any glass composition can be appropriately selected according to the required properties for controlling the resistance value. Further, in order to adjust the resistance value or to control other electrical characteristics required for the resistor, a metal oxide can be added according to the required characteristics. Moreover, in order to adjust these electrical characteristics, it is not necessary to limit to an oxide, and a metal may be added depending on the application. When a resistance of about 0.1Ω or less is required, An insulating oxide may be used.
[0029]
The resistance value can be controlled by the mixing ratio of the conductive oxide and the insulating oxide, and can also be controlled by the film thickness. Furthermore, the resistance value can also be controlled by the glass composition.
[0030]
The third conductive layer 24 is made of at least one metal (including alloy) of Pd, Ag, Au, Pt, Rh, Ru, Rh, and Ir, preferably an Ag-based alloy, and more preferably Ag.
[0031]
The first conductive layer 20 and the third conductive layer 24 are made of glass to improve the sinterability of the conductive material and to secure the adhesion between the element body 10 or each of the conductive layers 20 to 24. Contained. The composition of this glass need not be particularly limited, but preferably contains manganese oxide. The content of manganese oxide is preferably 0 to 40% by weight of the whole glass, and more preferably 0.01 to 20% by weight.
[0032]
By containing manganese oxide in the glass, the sinterability of the first conductive layer 20 and the third conductive layer 24 is remarkably improved, and the plating solution suppresses penetration into the terminal when forming the plating layer 26 and the like. Can be sure to do. As a result, it is possible to suppress fluctuations in resistance before and after plating.
[0033]
In the present embodiment, the plating layer 26 is formed on the third conductive layer 24 as necessary. The plating layer 26 may use either a dry method represented by sputtering or the like, or a wet method performed in a plating solution, but a conventionally known wet method, specifically, an electrolytic plating method, An electroless plating method can be used, and an electrolytic plating method is preferable.
[0034]
When the plating layer is formed on the terminal electrode by the electrolytic plating method, it is usually formed in the order of Ni and Sn or Ni and Sn—Pb solder plating from the terminal electrode. It is preferable to form a plating layer in the order of Sn and Sn. Although the thickness of a plating layer is not specifically limited, Usually, it is about 0.1-20 micrometers in total.
[0035]
In the multilayer ceramic capacitor 2 of the present embodiment, since the third conductive layer 24 in the terminal electrode is a sintered metal layer, it can be easily plated in the electrolytic plating process, and the plating solution into the terminal electrode Can also be suppressed. Therefore, the fluctuation of the resistance value of the second conductive layer can be suppressed before and after plating. For the same reason, since moisture penetration can be suppressed even in the moisture resistance load test, it is extremely stable over time.
[0036]
The multilayer ceramic capacitor 2 of this embodiment is manufactured as follows. First, a sintered body chip that is the element body 10 of the multilayer ceramic capacitor is manufactured. The method for producing a sintered body chip is obtained by obtaining a laminate of the dielectric layer 4 and the internal electrode layers 6 and 8 by a printing method or a green sheet method and then sintering after removing the binder according to a conventional method. .
[0037]
Thereafter, external terminal electrodes 12 and 14 are formed on both end surfaces of the element body 10 where the end portions of the internal electrode layers 6 and 8 are exposed. In forming the external terminal electrodes 12 and 14, first, the first conductive layer paste is applied to both end faces of the element body 10 and dried to remove the binder (binder removal). The binder removal conditions are not particularly limited, but it is usually preferable to carry out in air for about 300 to 600 ° C. for about 1 to 60 minutes. During this removal, Ni which is the internal electrode layers 6 and 8 is oxidized. Therefore, a reduction treatment is performed to reduce the oxidized Ni. The reduction is not particularly limited, but about 250 to 600 ° C., about 1 to 60 minutes, N₂And H₂It is preferable to carry out in a mixed atmosphere.
[0038]
Then neutral or N₂And H₂Baking is performed on the element body 10 in a reducing atmosphere, which is a mixed gas. The baking temperature is not particularly limited, and is preferably about 600 to 1200 ° C. and about 1 to 60 minutes.
[0039]
Next, a second conductive layer paste is applied onto the first conductive layer 20, dried, and baked. The baking conditions are not particularly limited, and are preferably about 600 to 1000 ° C. and about 1 to 60 minutes, and the atmosphere is preferably an oxidizing atmosphere, particularly in the air.
[0040]
Next, a third conductive layer paste is applied onto the second conductive layer 22, dried, and baked. The baking conditions may be the same as those for the second conductive layer 22. Note that the baking process may be performed simultaneously after the application and drying of the third conductive layer paste, without baking immediately after the application and drying of the second conductive layer paste. The baking process in this case is performed in an oxidizing atmosphere, particularly in air.
[0041]
Also, the same effect can be obtained by baking the first conductive layer 20 and the second conductive layer 22 at the same time, or baking the first to third conductive layers at the same time. The baking process in this case is performed in a reducing atmosphere.
Details of the manufacturing method will be described below.
[0042]
[Dielectric layer paste]
The dielectric layer paste is manufactured by kneading a dielectric material and an organic vehicle. As the dielectric material, a powder corresponding to the composition of the dielectric layer is used. The dielectric material is not particularly limited, and various dielectric materials may be used. For example, a titanium oxide-based oxide, a titanium-based composite oxide, or a mixture thereof is preferable. As the titanium oxide-based oxide, NiO, CuO, Mn are optionally used.₃O₄, Al₂O₃, MgO, SiO₂TiO to which a total of 0.001 to 30% by weight is added₂-Based oxides are exemplified, and titanium-based composite oxides include barium titanate BaTiO.₃Etc. The atomic ratio of Ba / Ti is preferably about 0.95 to 1.20, and BaTiO₃Includes MgO, CaO, Mn₃O₄, Y₂O₃, V₂O₅, ZnO, ZrO₂, Nb₂O₅, Cr₂O₃, Fe₂O₃, P₂O₅, Na₂O, K₂O or the like may be added in a total amount of about 0.001 to 30% by weight. In addition, (BaCa) SiO for adjusting the firing temperature and the linear expansion coefficient₂Glass such as glass may be added to the dielectric layer paste.
[0043]
The method for producing the dielectric material is not particularly limited. For example, when barium titanate is used, hydrothermally synthesized BaTiO 3 is used.₃In addition, a method of mixing the subcomponent raw materials can be used. BaCO₃And TiO₂Alternatively, a dry synthesis method may be used in which a mixture of a raw material and a subcomponent raw material is calcined to cause a solid phase reaction. Further, a mixture of a precipitate obtained by a coprecipitation method, a sol-gel method, an alkali hydrolysis method, a precipitation mixing method and the like and a subcomponent material may be calcined and synthesized. In addition, as a subcomponent, at least 1 or more types, such as an oxide and various compounds which become an oxide by baking, for example, carbonate, an oxalate, a hydroxide, an organometallic compound, etc., can be used.
The average particle size of the dielectric material may be determined according to the average crystal particle size of the target dielectric layer, but usually a powder having an average particle size of about 0.3 to 1.0 μm is used.
The dielectric layer paste is manufactured by kneading a dielectric material and an organic vehicle.
[0044]
The organic vehicle is obtained by dissolving a binder in an organic solvent. The binder used for the organic vehicle is not particularly limited, and may be appropriately selected from usual various binders such as ethyl cellulose. Further, the organic solvent to be used is not particularly limited, and may be appropriately selected from various organic solvents such as terpineol, butyl carbitol, acetone, and toluene depending on the printing method, the sheet method, and the method to be used.
[0045]
The thickness per layer of the dielectric layer is not particularly limited, but is usually about 1.5 to 20 μm. Moreover, the number of laminated dielectric layers is usually about 100 to 300.
[0046]
[Internal electrode layer paste]
The conductive material of the internal electrode layer paste is not particularly limited, but is preferably composed of at least one selected from Ni and Cu. Moreover, an inexpensive base metal can be used by using a material having a reduction resistance as the dielectric layer constituent material. For this reason, Ni or Ni alloy is particularly preferable as the conductive material. The Ni alloy is preferably an alloy of Ni and one or more elements selected from Mn, Cr, Co, Al, etc., and the Ni content in the alloy is preferably 95% by weight or more. In addition, in Ni or Ni alloy, various trace components, such as P, may be contained by about 0.1 wt% or less.
[0047]
The internal electrode layer paste is prepared by kneading the above-mentioned various conductive metals and alloys, or various oxides, organometallic compounds, resinates, and the like that become the above-described conductive material after firing and the above-described organic vehicle.
The thickness of the internal electrode may be appropriately determined according to the use, but is preferably about 0.5 to 5 μm.
[0048]
[First conductive layer paste]
The first conductive layer paste includes a conductive material, glass frit, and an organic vehicle. The conductive material is selected from at least one of Ag, Au, Pt, Pd, Ru, Ir, and Rh, preferably Ag, Pd, or an alloy thereof, and particularly preferably Ag and Pd. Glass frit is added to these conductive materials in order to ensure adhesion to the sintering aid or chip body.
[0049]
The average particle size of the conductive material is 0.01 to 30 μm. When the particle size is smaller than this, the aggregation of the conductive material particles becomes severe, and the first conductive layer is liable to crack when the first conductive layer layer paste is applied, dried, or baked. When the diameter is large, pasting becomes difficult.
[0050]
The average particle size of the glass frit is 0.01 to 30 μm. If the particle size is smaller than this, sintering of the conductive material becomes non-uniform, causing cracks in the terminal electrode. If it is larger than this, the dispersion of the glass deteriorates, and the first conductive layer 20 and the element body 10 are deteriorated. Adhesiveness with is reduced.
[0051]
The conductive material and glass frit are dispersed in a vehicle to obtain a first conductive layer paste.
The glass frit composition is not particularly limited. However, since it is necessary to bake in a neutral or reducing atmosphere, it is necessary to perform the function as glass even in such an atmosphere. For example, silicate glass {(SiO₂: 20-80% by weight, Na₂O: 80 to 20% by weight) and (SiO₂: 7 to 63% by weight, ZnO: 37 to 93% by weight)}, borosilicate glass (B₂O₃: 5 to 50% by weight, SiO₂: 5-70 wt%, PbO: 1-10 wt%, K₂O: 1 to 15% by weight), alumina silicate glass (Al₂O₃: 1 to 30% by weight, SiO₂: 10 to 60% by weight, Na₂O: 5 to 15% by weight, CaO: 1 to 20% by weight, B₂O₃: One to two or more kinds of glass frit selected from 5 to 30% by weight may be used.
[0052]
For such glass, if necessary, CaO: 0.01 to 50 wt%, BaO: 0.01 to 50 wt%, MgO: 0.01 to 5 wt%, ZnO: 0.01 to 70 wt% %, PbO: 0.01 to 5% by weight, Na₂O: 0.01 to 10% by weight, K₂O: 0.01 to 10% by weight, MnO₂: An additive such as 0.01 to 40% by weight may be mixed so as to have a predetermined composition.
The content of the glass with respect to the metal component which is a conductive material is not particularly limited, but is usually about 0.5 to 15% by weight with the metal component being 100% by weight.
The organic vehicle described above may be used as the organic vehicle.
[0053]
[Second conductive layer paste]
The second conductive layer paste includes a conductive material, glass frit, and an organic vehicle. This conductive material is selected from at least one of ruthenium oxide, ruthenium oxide compounds and graphite, but ruthenium oxide (RuO).₂) Is preferable. Glass frit is added to the second conductive layer paste to control the resistance value, to ensure the adhesion of the conductive material sintering aid, or the element body 10 and the first conductive layer 20.
[0054]
The average particle diameter of the conductive material is preferably 0.01 to 30 μm. When the particle diameter is smaller than this, the aggregation of the conductive material particles becomes intense, and the second conductive layer is likely to crack when the first conductive layer paste is applied, dried, or baked. When is large, pasting becomes difficult. The average particle size of the glass frit is 0.01 to 30 μm. If the particle size is smaller than this, sintering of the conductive material becomes non-uniform, which not only causes cracks in the second conductive layer, but also increases the variation in resistance value. The dispersion of the resistance becomes worse, and the variation of the resistance value also increases.
The conductive material and glass frit are dispersed in a vehicle to obtain a second conductive layer paste.
[0055]
The glass frit composition is not particularly limited, and the same glass frit composition as that of the first conductive layer may be used, and the glass composition can be appropriately selected depending on a desired resistance value.
The organic vehicle described above may be used as the organic vehicle.
[0056]
[Third conductive layer paste]
The third conductive layer paste includes a conductive material, glass frit, and an organic vehicle. The conductive material is selected from at least one of Ag, Au, Pt, Pd, Ru, Ir, and Rh, but is preferably Ag or an Ag-based alloy, and particularly preferably Ag. Glass frit is added to these conductive materials in order to ensure adhesion between the sintering aid or the chip body and the second conductive layer.
[0057]
The average particle diameter of the conductive material is 0.01 to 30 μm. When the particle size is smaller than this, the aggregation of the conductive material particles becomes severe, and the third conductive layer is liable to crack when the third conductive layer paste is applied, dried, or baked. When is large, pasting becomes difficult. The average particle size of the glass frit is 0.01 to 30 μm. If the particle size is smaller than this, sintering of the conductive material becomes non-uniform, causing cracks in the terminal electrode, and if it is larger than this, the dispersion of the glass is deteriorated, and the second conductive layer 22 and / or the raw material is not. Adhesiveness with the body main body 10 falls.
[0058]
The conductive material and glass frit are dispersed in a vehicle to obtain a third conductive layer paste.
The glass frit composition is not particularly limited, but more preferably contains manganese oxide.
[0059]
[Content of organic vehicle]
There is no restriction | limiting in particular in content of the organic vehicle in each above-mentioned paste, What is necessary is just to set normal content, for example, about 1 to 5 weight% for a binder, and 10 to 50 weight% for a solvent. Each paste may contain an additive selected from various dispersants, plasticizers, dielectrics, insulators, and the like as necessary. The total content of these is preferably 10% by weight.
[0060]
[Production of green chip]
When using the printing method, the dielectric paste and the internal electrode paste are printed on a substrate such as PET. At this time, lamination is performed so that one of the end portions of the internal electrode paste is alternately exposed to the outside from the end portion of the dielectric paste. Thereafter, thermocompression bonding is performed, cutting into a predetermined shape to form a chip, and then peeling from the substrate to obtain a green chip.
[0061]
When using the sheet method, a dielectric layer paste is used to form a green sheet, the internal electrode layer paste is printed on the green sheet, and these layers are alternately stacked, and cut into a predetermined shape. Use green chips.
[0062]
[Debinding process]
The conditions for the debinding treatment performed before firing may be normal, but when a base metal such as Ni or Ni alloy is used for the conductive material of the internal electrode layer, it is particularly preferable to perform under the following conditions.
[0063]
Temperature increase rate: 5 to 300 ° C./hour, particularly 10 to 100 ° C./hour,
Holding temperature: 200 to 400 ° C./hour, in particular 250 to 300 ° C./hour,
Temperature holding time: 0.5 to 24 hours, especially 5 to 20 hours,
Atmosphere: in the air.
[0064]
[Baking process]
The atmosphere during firing of the green chip may be appropriately selected according to the type of the conductive material of the internal electrode paste, but when a base metal such as Ni or Ni alloy is used as the conductive material, the firing atmosphere is N.₂As the main component and H₂1 to 10% by volume and H obtained by water vapor pressure at 10 to 35 ° C.₂What mixed O gas is preferable. Oxygen partial pressure is 10^-3-10^-8Pa is preferable. When the oxygen partial pressure is less than the above range, the conductive material in the internal electrode layer may be abnormally sintered and may be interrupted. Further, when the oxygen partial pressure exceeds the above range, the internal electrode layer tends to be oxidized.
[0065]
The holding temperature during firing is preferably 1100 to 1400 ° C, particularly preferably 1200 to 1300 ° C. If the holding temperature is less than the above range, the densification is insufficient, and if it exceeds the above range, the internal electrode layer tends to be interrupted. The temperature holding time during firing is preferably 0.5 to 8 hours, particularly 1 to 3 hours.
[0066]
[Annealing process]
When firing in a reducing atmosphere, it is preferable to anneal the element body 10 of the multilayer capacitor. Annealing is a process for re-oxidizing the dielectric layer 4, whereby the accelerated life of the insulation resistance can be significantly prolonged.
[0067]
The oxygen partial pressure in the annealing atmosphere is 10^-3Pa or more, especially 10^-3-10^-1Pa is preferable. If the oxygen partial pressure is less than the above range, reoxidation of the dielectric layer is difficult, and if it exceeds the above range, the internal electrode layer is oxidized.
[0068]
The annealing holding temperature is preferably 1100 ° C. or lower, particularly 500 to 1000 ° C. When the holding temperature is lower than the above range, the dielectric layer is not sufficiently oxidized, and the accelerated lifetime of the insulation resistance tends to be shortened. It reacts with the dielectric substrate and shortens the accelerated life. Note that the annealing step may be composed only of temperature rise and temperature drop. In this case, it is not necessary to take a temperature holding time, and the holding temperature is synonymous with the maximum temperature. The temperature holding time is preferably 0 to 20 hours, particularly 2 to 10 hours. The atmosphere gas is N₂And humidified H₂It is preferable to use a gas.
[0069]
In each process of debinding, firing and annealing described above, N₂, H₂For example, a wetter or the like may be used to wet the gas or the mixed gas. The water temperature in this case is preferably about 5 to 75 ° C.
[0070]
The binder removal step, the firing step, and the annealing step may be performed continuously or independently.
When these are performed continuously, the atmosphere may be changed independently without cooling after the binder removal treatment. When performing these continuously, after debinding, change the atmosphere without cooling, then raise the temperature to the firing holding temperature, perform firing, then cool and reach the holding temperature in the annealing process It is preferable to perform annealing by changing the atmosphere.
[0071]
Moreover, when performing these independently, in a binder removal process, it heats up to predetermined | prescribed holding | maintenance temperature, and after holding | maintaining for predetermined time, it falls to room temperature. The binder removal atmosphere at that time is the same as in the case of continuous operation. Alternatively, the debinding step and the firing step may be performed continuously, and only the annealing step may be performed independently, or only the debinding step may be performed independently, and the firing step and the annealing step performed continuously. You may make it do.
[0072]
[Formation of first conductive layer]
The first conductive layer paste is applied to the sintered body chip. Although it does not specifically limit as an application | coating process, The dipping method etc. should just be used. The application amount of the first conductive layer paste is not particularly limited, and may be appropriately adjusted depending on the size of the sintered body chip to be applied, but is usually about 5 to 100 μm. After applying the terminal electrode paste, it is dried. Drying is preferably performed at about 60 to 150 ° C. for about 10 minutes to 1 hour.
[0073]
After the first conductive layer paste is applied and dried as described above, the chip body is baked. The baking condition is, for example, N₂Neutral atmosphere or N₂And H₂It is preferable to carry out by maintaining at 600 to 1200 ° C. for about 0 to 1 hour in a reducing atmosphere such as a mixed gas.
[0074]
[Formation of second conductive layer]
On the first conductive layer formed as described above, the second conductive layer paste is applied so as to completely cover the first conductive layer. Although it does not specifically limit as an application | coating process, The dipping method etc. should just be used. The coating amount of the second conductive layer paste is not particularly limited and may be appropriately adjusted within a range in which a desired resistance value can be obtained, but is usually about 5 to 100 μm. After applying the second conductive layer paste, it is dried. Drying is preferably performed at about 60 to 150 ° C. for about 10 minutes to 1 hour.
[0075]
After applying and drying the second conductive layer paste as described above, baking is performed. It is preferable to perform baking conditions by hold | maintaining for about 0 to 1 hour at 600 to 1000 degreeC in the air, for example.
[0076]
[Formation of third conductive layer]
A third conductive layer paste is applied on the second conductive layer thus formed. Although it does not specifically limit as an application | coating process, The dipping method etc. should just be used. The application amount of the third conductive layer paste is not particularly limited, and may be appropriately adjusted depending on the size of the element body 10, but is usually about 5 to 100 μm. After applying the third conductive layer paste, it is dried. Drying is preferably performed at about 60 to 150 ° C. for about 10 minutes to 1 hour.
[0077]
After applying and drying the third conductive layer paste as described above, baking is performed. It is preferable to perform baking conditions by hold | maintaining for about 0 to 1 hour at 600 to 1000 degreeC in the air, for example. Note that the baking process may be performed simultaneously after the application and drying of the third conductive layer paste, without baking immediately after the application and drying of the second conductive layer paste.
[0078]
[Plating layer]
If necessary, Ni and Sn layers or Sn—Pb alloy layers are formed on the terminal electrodes 12 and 14 by electrolytic plating. The thickness of the plating layer 26 is not particularly limited, but is usually about 0.1 to 20 μm.
[0079]
With such a configuration, the resistance value, that is, the ESR can be controlled. The ESR is not particularly limited, but is about 0.5Ω to 10Ω, preferably 0.5 to 5Ω. By having an ESR within this range, sufficient performance as a capacitor for a regulator IC can be exhibited.
The present invention is not limited to the above-described embodiment, and can be variously modified within the scope of the present invention.
[0080]
For example, in the above-described embodiment, the main object is to form the resistor, which is the second conductive layer 22 in the terminal electrode, in an oxidizing atmosphere, but the first conductive layer 20 to the third conductive layer 24 are formed. All can be formed by baking in a neutral or reducing atmosphere. In this case, various resistor materials can be used as the resistor material in the second conductive layer 22. As the resistor in this case, for example, TaN, Ta₂N, LaB₆, WC, MoSi₂, TaSi₂, SnO₂, Ta₂O₅Etc. can be mentioned as examples.
[0081]
【Example】
Hereinafter, although this invention is demonstrated based on a more detailed Example, this invention is not limited to these Examples.
Example 1
BaCO as the main raw material for the dielectric layer₃(Average particle size: 2.0 μm) and TiO₂(Average particle diameter: 2.0 μm) was prepared. The atomic ratio Ba / Ti is 1.00. In addition to this, 100% by weight of BaTiO.₃In contrast, MnCO as an additive₃0.2 wt%, MgCO₃0.2% by weight, Y₂O₃2.1 wt%, (BaCa) SiO₃Of 2.2% by weight were prepared.
[0082]
These raw material powders were mixed in an underwater ball mill and dried. The obtained mixed powder was calcined at 1250 ° C. for 2 hours. The calcined powder was pulverized with an underwater ball mill and dried. To the obtained calcined powder, an acrylic resin as an organic binder and methylene chloride and acetone as an organic solvent were added and further mixed to obtain a dielectric slurry. The obtained dielectric slurry was made into a dielectric green sheet by a doctor blade method.
[0083]
Ni powder (average particle size: 0.8 μm) was prepared as an internal electrode material, and ethyl cellulose as an organic binder and terpineol as an organic solvent were added thereto, and the mixture was kneaded using three rolls to obtain an internal electrode paste.
[0084]
As the conductive material of the first conductive layer, 30% by weight of Ag powder (average particle size: 5.0 μm) and 70% by weight of Pd powder (average particle size: 1.0 μm) are selected, and these conductive powders are 100% by weight. In contrast, 5% by weight of zinc-based glass frit or zinc-based manganese-containing glass having an average particle size of 2.0 μm is added, acrylic resin as an organic binder and terpineol as an organic solvent are added thereto, and kneaded using three rolls The first conductive layer paste was obtained.
[0085]
As the conductive material of the second conductive layer, RuO₂(Average particle diameter: 1.0 μm), and mainly for adjusting the resistance value, as an insulating oxide, a zinc-based glass (ZnO: 65% by weight, B₂O₃: 22% by weight, SiO₂: 13 wt%) was added in an amount of 50 to 500 wt%, and an organic binder, an acrylic resin, and terpineol as an organic solvent were added thereto, and the mixture was kneaded using three rolls to obtain a second conductive layer paste.
[0086]
As the conductive material of the third conductive layer, Ag powder (average particle size: 0.5 μm) is selected, and zinc-based glass frit or zinc-based manganese containing an average particle size of 2.0 μm is contained with respect to 100% by weight of the conductive powder. 5% by weight of glass was added, acrylic resin as an organic binder and terpineol as an organic solvent were added thereto, and the mixture was kneaded using three rolls to obtain a third conductive layer paste.
[0087]
In order to obtain a predetermined thickness, several dielectric green sheets are laminated, and the ends of the internal electrode paste are alternately exposed to the outside from the ends of the dielectric layer green sheets by screen printing. 200 printed green sheets were laminated and thermocompression bonded. Next, the chip shape after firing was cut so as to be 2.0 mm long × 1.2 mm wide × 1.2 mm thick to obtain a green chip.
[0088]
The obtained green chip was humidified with N₂+ H₂(H₂: 3% by volume) H kept in an atmosphere at 1300 ° C. for 3 hours, fired, and further humidified₂Partial pressure of oxygen containing gas 10^-2The chip was held at 1000 ° C. for 2 hours in an atmosphere of Pa to obtain a chip sintered body. After applying the first conductive layer paste to both ends of the obtained sintered body, drying, removing the binder in the air, and performing a reduction treatment to reduce Ni, N₂-H₂The first conductive layer was obtained by holding at 950 ° C. for 10 minutes in the atmosphere. The second conductive layer paste was applied onto the formed first conductive layer, dried, and held in air at 850 ° C. for 10 minutes to obtain a second conductive layer.
The third conductive layer paste was applied onto the formed second conductive layer, dried, and held in air at 650 ° C. for 10 minutes to obtain a third conductive layer.
[0089]
Thereafter, a plating film was formed on the third conductive layer by electrolytic plating in the order of Ni and Sn. The capacitance of the obtained sample was 2.0 μF as designed.
[0090]
Table 1 shows the ESR values of the electronic parts manufactured as described above. The number of each measured is 50 and the average value is shown. As the glass in the first conductive layer and the third conductive layer, zinc-based glass (ZnO: 65 wt%, B₂O₃: 22% by weight, SiO₂: 13 wt%) and the conductive material of the second conductive layer is RuO₂As the glass in the second conductive layer, the above zinc-based glass was used. Changes in ESR before and after plating are numbered in advance on the body before plating. ESR is measured before and after plating, and if there is a fluctuation of ± 1.0 mΩ or more, it is judged that there is a fluctuation. Was measured.
[0091]
[Table 1]

[0092]
From the results shown in Table 1, glass and RuO in the second conductive layer₂It was confirmed that the ESR can be controlled by adjusting the weight ratio. It was also confirmed that there was little fluctuation in ESR before and after plating.
[0093]
Further, when the sample of this example was used as a smoothing capacitor of the regulator IC and operated at 100 kHz, it operated normally without causing voltage fluctuations such as oscillation.
[0094]
In addition, the sample of this example was subjected to a high-temperature load test (85 ° C., voltage application twice as high as the rating) and a moisture resistance load test (85 ° C., 85%, rated voltage application), which are capacitor acceleration tests. There was no change in ESR variation or other electrical characteristics.
[0095]
Example 2
Capacitor in the same manner as in Example 1 except that baking was performed simultaneously in air after application and drying of the third conductive layer paste, without baking immediately after application and drying of the second conductive layer paste. Samples were prepared and subjected to similar tests. The results are shown in Table 2.
[0096]
[Table 2]

[0097]
As shown in Table 2, as compared with Example 1, it was confirmed that the number of ESR fluctuations before and after plating was further reduced, and the control characteristics and stability of ESR were further increased.
[0098]
Comparative Example 1
A capacitor sample was prepared in the same manner as in Example 1 except that the third conductive layer 24 shown in FIG. 1 was not formed. However, since the second conductive layer 22 is composed of oxide, The plating layer 26 could not be formed. Although it is possible to form a plating layer by using electroless plating, the resistance variation becomes large, which is not practical.
Comparative Example 2
Except not forming the 1st conductive layer 20 shown in FIG. 1, the capacitor | condenser sample was produced similarly to the said Example 1, and the same test was done.
[0099]
Since the second conductive layer 22 is formed directly on the capacitor body 10 without forming the first conductive layer 20, electrical connection with Ni as the internal electrode cannot be ensured, and the static electricity as designed. Capacitance and other electrical characteristics could not be obtained.
[0100]
Example 3
A similar tendency was observed when a capacitor sample was prepared in the same manner as in Example 1 except that strontium-based glass was used as the glass composition in the second conductive layer, and a similar test was performed.
[0101]
Example 4
Bi as a conductive material in the second conductive layer₂Ru₂O₇A similar tendency was also observed when a capacitor sample was prepared in the same manner as in Example 1 and the same test was performed, except that was used.
Moreover, the capacitor sample of this example was subjected to a moisture resistance load test (85 ° C./85% RH: rated voltage application) for 1000 hours, and the rate of change of ESR before and after that was measured, and was within ± 0.5% It was confirmed that stable ESR was obtained. As a conductive material in the second conductive layer, RuO₂When the same moisture resistance load test was performed on the capacitor sample of Example 1 using the same, the variation rate of ESR was ± 3%.
[0102]
Example 5
As glass of the first conductive layer and the third conductive layer, zinc-based manganese-containing glass (ZnO: 60% by weight, B₂O₃: 20% by weight, SiO₂Table 3 shows the results of producing a capacitor sample in the same manner as in Example 1 except that: 10 wt% and MnO: 10 wt% were used.
[0103]
[Table 3]

[0104]
As shown in Table 3, the use of zinc-based manganese-containing glass further reduces the number of ESR fluctuations before and after plating, and further increases the control characteristics and stability of ESR. It could be confirmed.
[0105]
Example 6
A capacitor sample was prepared in the same manner as in Example 1 except that graphite / carbon (average particle size: 1.1 μm) was used as the conductive material in the second conductive layer. Table 4 shows.
[0106]
[Table 4]

[0107]
Example 7
As in Example 1, except that an alloy powder of Ag—Pd (average particle size: 0.8 μm) having a composition ratio of Ag and Pd of 30:70 was used as the conductive material of the first conductive layer. The same tendency was observed when a capacitor sample was prepared and the same test was performed.
Moreover, in the capacitor sample of Example 7, the ESR variation (CV value) was 5.5%, compared with Example 1 (mixed powder of Ag and Pd) in which the CV value was 13%. It was confirmed that it could be further reduced. In Examples 1 and 7, the CSR value of ESR is the same as that of glass in the second conductive layer and RuO.₂When the weight ratio is 3.0, 50 samples before plating were prepared, their ESR was measured, and the variation was determined.
[0108]
【The invention's effect】
As described above, according to the present invention, a resistance function is imparted to an external terminal electrode portion of an electronic component such as a multilayer ceramic capacitor, resistance does not vary due to plating, and resistance does not change with time. It is possible to realize an electronic component having a property, more specifically, a CR composite electronic component.
[Brief description of the drawings]
FIG. 1 is a cross-sectional view of a main part of a multilayer ceramic capacitor as an electronic component according to an embodiment of the present invention.
[Explanation of symbols]
2 ... Multilayer ceramic capacitor
4 ... Dielectric layer
6, 8 ... Internal electrode layer
10 ... Element body
12, 14 ... External electrode terminals
20 ... 1st conductive layer
22 ... Second conductive layer
24 ... Third conductive layer
26 ... Plating layer

Claims (14)

An element body in which dielectric layers and internal electrode layers are alternately laminated;
An electronic component having an external terminal electrode formed on the outer surface of the element body,
The external terminal electrode is
The directly formed on the outer surface of the device body so as to at least partially electrically connected to the internal electrodes, a first conductive layer made of a material hardly oxidizable,
A second conductive layer formed on an outer surface of the first conductive layer and mainly including a mixture of a conductive material and an insulating material;
Formed on the outer surface of the second conductive layer, it has a third conductive layer formed of a material of the hardly oxidizable,
The hardly oxidizable material is composed of one or more metals selected from Pd, Ag, Pt, Au, Rh, Ir, and Ru, or an alloy of two or more thereof.
An electronic component, wherein the conductive material includes graphite . The electronic component according to claim 1 , wherein the insulating substance includes glass and a metal oxide . The second conductive layer, the electronic component according to claim 1 or 2, characterized in that functions as a resistor to a higher resistance than the resistance of the first conductive layer and the third conductive layer. Electronic component according to any one of claims 1 to 3 having an average particle diameter of the particles forming the first conductive layer and the third conductive layer is characterized in that it is a 0.1 to 30 [mu] m. The conductive material particles forming the second conductive layer have an average particle size of 0.01 to 10 μm, and the insulating material particles have an average particle size of 0.01 to 10 μm. Item 5. The electronic component according to any one of Items 1 to 4 . Electronic component according to any one of claims 1 to 5, wherein the first conductive layer and the third conductive layer is characterized by containing the glass. The electronic component according to claim 6 , wherein the glass of the first conductive layer and the third conductive layer contains manganese oxide. 8. The electronic component according to claim 7 , wherein the content of manganese oxide in the glass containing manganese oxide is 0 to 40% by weight (excluding 0%) with 100% by weight of the entire glass. Electronic component according to any of claims 6-8 having an average particle diameter of the particles of the glass is characterized by a 0.01 to 30. Electronic component according to any one of claims 1 to 9, characterized in that the plating layer is formed on an outer surface of the third conductive layer. Electronic component according to any one of claims 1 to 10, wherein the inner electrode layer is characterized by containing Ni. Forming a device body in which dielectric layers and internal electrode layers are alternately laminated;
Applying and baking a first conductive layer paste containing a hardly oxidizable material on the outer surface of the element body to form a first conductive layer made of a hardly oxidizable material ;
Applying and baking a second conductive layer paste mainly containing a mixture of a conductive material and an insulating material on the outer surface of the first conductive layer to form a second conductive layer;
The outer surface of the second conductive layer, baking is applied to the third conductive layer paste containing the material for the hardly oxidizable, have a forming a third conductive layer,
The hardly oxidizable material is composed of one or more metals selected from Pd, Ag, Pt, Au, Rh, Ir, and Ru, or an alloy of two or more thereof.
The method for manufacturing an electronic component, wherein the conductive material includes graphite . Forming a device body in which dielectric layers and internal electrode layers are alternately laminated;
Applying and baking a first conductive layer paste containing a hardly oxidizable material on the outer surface of the element body to form a first conductive layer made of a hardly oxidizable material ;
Applying a second conductive layer paste mainly containing a mixture of a conductive material and an insulating material to the outer surface of the first conductive layer;
Applying a third conductive layer paste containing a hardly oxidizable material to the outer surface of the second conductive layer paste, followed by baking to form a second conductive layer and a third conductive layer. And
The hardly oxidizable material is composed of one or more metals selected from Pd, Ag, Pt, Au, Rh, Ir, and Ru, or an alloy of two or more thereof.
The method for manufacturing an electronic component, wherein the conductive material includes graphite . The baking of the first conductive layer paste is performed in an atmosphere other than an oxidizing atmosphere, and the baking of the second conductive layer paste and the third conductive layer paste is performed in an oxidizing atmosphere. 14. A method for producing an electronic component according to 12 or 13 .

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