JP4442264B2 - Conductive paste for internal electrodes and multilayer ceramic electronic components - Google Patents
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- Ceramic Capacitors (AREA)
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Description
本発明は、内部電極用導電性ペースト及び積層セラミック電子部品に関し、更に詳しくは、デラミネーションやクラックの発生を防止することができる内部電極用導電性ペースト及び積層セラミック電子部品に関するものである。 The present invention relates to a conductive paste for internal electrodes and a multilayer ceramic electronic component, and more particularly to a conductive paste for internal electrodes and a multilayer ceramic electronic component that can prevent the occurrence of delamination and cracks.
近年の電子部品の小型化に伴って積層セラミック電子部品の小型化も急速に進行している。特に、積層セラミックコンデンサは、小型且つ大容量化が急速に進んでおり、コンデンサの電気容量を増加させるため薄いセラミックグリーンシートの使用が急速に進んでいる。また、製造コストを低減するために、現在では内部電極用の導電性金属としてＮｉ等の卑金属を使用する傾向にある。 With recent miniaturization of electronic components, miniaturization of multilayer ceramic electronic components is also progressing rapidly. In particular, multilayer ceramic capacitors have been rapidly reduced in size and capacity, and thin ceramic green sheets have been rapidly used to increase the capacitance of the capacitors. Further, in order to reduce the manufacturing cost, a base metal such as Ni tends to be used as a conductive metal for the internal electrode at present.
積層セラミック電子部品、例えば積層セラミックコンデンサを製造する場合には、まず、セラミックグリーンシートを形成し、このセラミックグリーンシート上に導電性ペーストを塗布して乾燥した後、セラミックグリーンシートを複数枚積層し、圧着することにより生の積層体を作製する。次いで、生の積層体を所定の寸法のチップとして切断し、例えば４００℃以上で脱バインダした後、内部電極層が酸化されないように酸素分圧の低い非酸化性雰囲気下でチップを焼結して焼結体を得ている。 When manufacturing a multilayer ceramic electronic component, for example, a multilayer ceramic capacitor, first, a ceramic green sheet is formed, a conductive paste is applied on the ceramic green sheet and dried, and then a plurality of ceramic green sheets are stacked. A raw laminate is produced by pressure bonding. Next, the raw laminate is cut as a chip of a predetermined size, and after debinding at, for example, 400 ° C. or higher, the chip is sintered in a non-oxidizing atmosphere with a low oxygen partial pressure so that the internal electrode layer is not oxidized. To obtain a sintered body.
焼結工程では誘電体層と内部電極層を一体に焼成するため、誘電体層と内部電極層間の熱収縮挙動差によって歪が生じて誘電体層と内部電極層との間でデラミネーションやクラックが発生し易い。そこで、従来から、誘電体層と同種または類似のセラミック粉末を共材として導電性ペーストに添加して誘電体層と内部電極層間の熱収縮挙動差を抑制することによってデラミネーションやクラックの発生を抑制し、防止するようにしている。 In the sintering process, the dielectric layer and the internal electrode layer are integrally fired, so that distortion occurs due to the difference in thermal shrinkage between the dielectric layer and the internal electrode layer, resulting in delamination and cracks between the dielectric layer and the internal electrode layer. Is likely to occur. Therefore, conventionally, the same kind or similar ceramic powder as the dielectric layer is added to the conductive paste as a co-material to suppress the difference in thermal shrinkage behavior between the dielectric layer and the internal electrode layer, thereby preventing delamination and cracking. Suppress and prevent.
例えば、特許文献１にはニッケル粉末を主成分とし、平均粒径が最大でも０．１μｍの誘電体層と同じ組成物の共材を５〜３０ｗｔ％添加した内部電極用の導電体ペーストが提案されている。最大平均粒径が０．１μｍの共材を用いると、導電体ペースト中で共材がニッケル粉末中に分散し、焼結時にニッケル粉末の焼結収縮を抑制する効果が発現して焼成後の構造欠陥を抑制し、防止することができる。 For example, Patent Document 1 proposes a conductor paste for internal electrodes in which nickel powder is the main component and 5-30 wt% of a co-material of the same composition as the dielectric layer having a maximum average particle size of 0.1 μm is added. Has been. When a co-material having a maximum average particle size of 0.1 μm is used, the co-material is dispersed in the nickel powder in the conductive paste, and the effect of suppressing the sintering shrinkage of the nickel powder is exhibited during sintering. Structural defects can be suppressed and prevented.
また、特許文献２には共材として粒径分布中に２つの山を有するセラミック粉末を用いた導電ペーストが提案されている。この導電ペーストは、積層セラミックコンデンサの外部電極用として使用するものである。外部電極用の導電ペーストに粒径分布中に２つの山を有するセラミック粉末を添加して、外部電極とセラミック素体との結合強度を大きくすると共に外部電極の耐湿性を高めている。 Patent Document 2 proposes a conductive paste using ceramic powder having two peaks in the particle size distribution as a co-material. This conductive paste is used for an external electrode of a multilayer ceramic capacitor. A ceramic powder having two peaks in the particle size distribution is added to the conductive paste for the external electrode to increase the bonding strength between the external electrode and the ceramic body and to improve the moisture resistance of the external electrode.
しかしながら、特許文献１に記載の導電体ペーストの場合には、平均粒径の小さい共材を用いて導電体ペースト中での共材の分散性を高め、ニッケル粉末の焼結収縮を抑制して焼成後の構造欠陥を防止しているが、平均粒径の小さい共材では内部電極層中で、内部電極を挟む上下の誘電体層に対して柱構造を形成できないため、内部電極層と誘電体層との密着力が弱く、焼成終了後の降温時に内部電極層と誘電体層の界面においてデラミネーションやクラックが発生するという課題が新たに発生する。また、特許文献２に記載の導電ペーストの場合には、粒径分布中に２山を有する共材を用いて外部電極とセラミック素体との接合強度や外部電極の耐湿性を高めることができるが、共材の一方の山の平均粒径が２．５〜３．０μｍと大きいため、急激に薄層化が進む状況下では内部電極として用いることができない。このことは、特許文献２において外部電極とは異なる組成の導電ペーストを内部電極として使用していることからも推定される。 However, in the case of the conductor paste described in Patent Document 1, the dispersibility of the common material in the conductive paste is increased by using the common material having a small average particle diameter, and the sintering shrinkage of the nickel powder is suppressed. Although structural defects after firing are prevented, a co-material with a small average particle size cannot form a column structure in the internal electrode layer with respect to the upper and lower dielectric layers that sandwich the internal electrode. The adhesion with the body layer is weak, and a new problem arises that delamination and cracks occur at the interface between the internal electrode layer and the dielectric layer when the temperature is lowered after the firing. Further, in the case of the conductive paste described in Patent Document 2, the joint strength between the external electrode and the ceramic body and the moisture resistance of the external electrode can be increased by using a co-material having two peaks in the particle size distribution. However, since the average particle size of one of the peaks of the common material is as large as 2.5 to 3.0 μm, it cannot be used as an internal electrode under a situation where the layer thickness rapidly advances. This is also estimated from the fact that in Patent Document 2, a conductive paste having a composition different from that of the external electrode is used as the internal electrode.
本発明は、上記課題を解決するためになされたもので、積層セラミック電子部品を形成するセラミック層と１．０μｍ以下の厚さを有する内部電極層間のクラックやデラミネーション等の構造欠陥を防止すると共に内部電極とセラミック層の積層構造の破壊によるショート不良を防止することができる内部電極用導電性ペースト及び積層セラミック電子部品を提供することを目的としている。 The present invention has been made to solve the above-described problems, and prevents structural defects such as cracks and delamination between a ceramic layer forming a multilayer ceramic electronic component and an internal electrode layer having a thickness of 1.0 μm or less. Another object of the present invention is to provide a conductive paste for internal electrodes and a multilayer ceramic electronic component that can prevent a short circuit failure due to destruction of the multilayer structure of the internal electrode and the ceramic layer .
本発明の請求項１に記載の内部電極用導電性ペーストは、複数のセラミック層からなる積層体と、前記各セラミック層間に形成された内部電極と、を有する積層セラミック電子部品を構成する前記内部電極に用いられる内部電極用導電性ペーストであって、前記内部電極用導電性ペーストは、ニッケル粉末と、有機ビヒクルと、前記セラミック層と同一種またはた類似の組成からなるセラミック粉末と、を含有し、前記ニッケル粉末は、平均粒径が０．２〜１．０μｍであり、前記セラミック粉末は、平均粒径が０．２〜０．４μｍであるセラミック粉末Ａと、平均粒径が０．６〜０．８μｍであるセラミック粉末Ｂと、を含有し、且つ、前記セラミック粉末全量に対する前記セラミック粉末Ａの重量比（Ａ／（Ａ＋Ｂ））が０．３〜０．７であり、１．０μｍ以下の厚さの未焼成の内部電極として形成されることを特徴とするものである。 The internal electrode conductive paste according to claim 1 of the present invention is an internal electrode constituting a multilayer ceramic electronic component having a laminate composed of a plurality of ceramic layers and internal electrodes formed between the ceramic layers. An internal electrode conductive paste used for an electrode, wherein the internal electrode conductive paste contains nickel powder, an organic vehicle, and a ceramic powder having the same or similar composition as the ceramic layer. The nickel powder has an average particle size of 0.2 to 1.0 μm, and the ceramic powder has ceramic powder A having an average particle size of 0.2 to 0.4 μm and an average particle size of 0.1 μm. 6 to 0.8 μm of ceramic powder B, and the weight ratio (A / (A + B)) of the ceramic powder A to the total amount of the ceramic powder is 0.3 to 0.7. Ri, is characterized in Rukoto formed as green internal electrode of a thickness of less than 1.0 .mu.m.
また、本発明の請求項２に記載の積層セラミック電子部品は、複数のセラミック層からなる積層体と、前記各セラミック層間に形成された内部電極と、これらの内部電極に接続された外部電極と、を有し、前記内部電極は、請求項１に記載の導電性ペーストの焼結体からなることを特徴とするものである。 According to a second aspect of the present invention, there is provided a multilayer ceramic electronic component comprising: a laminate composed of a plurality of ceramic layers; an internal electrode formed between the ceramic layers; and an external electrode connected to the internal electrodes. The internal electrode is made of a sintered body of the conductive paste according to claim 1 .
而して、本発明の内部電極用導電性ペースト（以下、単に「導電性ペースト」と称す。）は、積層セラミック電子部品のセラミック層間の内部電極層を形成するためのものである。この導電性ペーストは、内部電極の導電性粉末としてニッケル粉末を含有している。ニッケル粉末の平均粒径は、特に制限されないが、内部電極の薄層化を勘案すると０．２〜１．０μｍの範囲が好ましい。平均粒径が０．２μｍ未満ではニッケル粉末が凝集し易いため好ましくなく、平均粒径が１．０μｍを超えると内部電極を薄層化する上で好ましくない。 Thus, the internal electrode conductive paste (hereinafter simply referred to as “conductive paste”) of the present invention is for forming an internal electrode layer between ceramic layers of a multilayer ceramic electronic component. This conductive paste contains nickel powder as the conductive powder of the internal electrode. The average particle diameter of the nickel powder is not particularly limited, but is preferably in the range of 0.2 to 1.0 μm in consideration of thinning of the internal electrode. If the average particle size is less than 0.2 μm, the nickel powder tends to aggregate, which is not preferable. If the average particle size exceeds 1.0 μm, it is not preferable for thinning the internal electrode.
また、上記導電性ペーストに用いられる有機ビヒクルは、バインダと溶剤とを混合したもので、従来公知のものを用いることによってニッケル粉末をペースト化することができる。バインダとしては、例えばエチルセルロース、アクリル樹脂、ポリビニルブチラール、メタクリル樹脂等を用いることが好ましい。また、溶剤としては、例えばテルピネオール、ブチルカルビトール、ブチルカルビトールアセテート、アルコール類を用いることが好ましい。また、可塑剤として、例えばＤＯＰ（ジオクチルフタレート）、オクタンジオール等を用いることが好ましい。また、有機ビヒクルには必要に応じて分散剤、界面活性剤等を適宜添加しても良い。 The organic vehicle used for the conductive paste is a mixture of a binder and a solvent, and nickel powder can be made into a paste by using a conventionally known one. As the binder, for example, ethyl cellulose, acrylic resin, polyvinyl butyral, methacrylic resin, or the like is preferably used. As the solvent, for example, terpineol, butyl carbitol, butyl carbitol acetate, and alcohols are preferably used. Moreover, as a plasticizer, it is preferable to use DOP (dioctyl phthalate), octanediol, etc., for example. Moreover, you may add a dispersing agent, surfactant, etc. to an organic vehicle suitably as needed.
上記導電性ペーストに用いられるセラミック粉末は、セラミック層の共材となるもので、セラミック層と同一種または類似のセラミック粉末が好ましい。このセラミック粉末は、平均粒径が０．２〜０．４μｍのセラミック粉末Ａと、平均粒径が０．６〜０．８μｍのセラミック粉末Ｂとを含んでいる。 The ceramic powder used for the conductive paste is a common material for the ceramic layer, and the same or similar ceramic powder as the ceramic layer is preferable. This ceramic powder contains ceramic powder A having an average particle diameter of 0.2 to 0.4 μm and ceramic powder B having an average particle diameter of 0.6 to 0.8 μm.
セラミック粉末Ａは、平均粒径が０．２〜０．４μｍである。セラミック粉末Ａは、ニッケル粉末の平均粒径（０．２〜１．０μｍ）より比較的小さく、導電性ペースト中に分散してニッケル粉末粒子間の隙間に入り込み易いため、ニッケル粉末粒子間の隙間を埋めて焼成時の昇温段階においてニッケル粉末の焼結収縮を抑制する、所謂ピンニング効果を発現することができる。 The ceramic powder A has an average particle size of 0.2 to 0.4 μm. Since the ceramic powder A is relatively smaller than the average particle diameter (0.2 to 1.0 μm) of the nickel powder and is easily dispersed into the gap between the nickel powder particles by being dispersed in the conductive paste, the gap between the nickel powder particles. A so-called pinning effect that suppresses the sintering shrinkage of the nickel powder in the temperature rising stage during firing can be exhibited.
従って、セラミック粉末Ａによって焼成時における導電性ペーストの熱収縮率を調整することができ、もって昇温段階における内部電極層とセラミック層との間の熱収縮差を抑制してデラミネーションやクラックを抑制することができる。 Therefore, the ceramic powder A can adjust the thermal shrinkage rate of the conductive paste at the time of firing, thereby suppressing the thermal shrinkage difference between the internal electrode layer and the ceramic layer in the temperature rising stage, thereby preventing delamination and cracks. Can be suppressed.
セラミック粉末Ａでピンニング効果を発現させるためには、セラミック粉末Ａの平均粒径が小さい方が好ましいが、平均粒径が０．２μｍ未満ではセラミック粉末が凝集して分散性が著しく低下して積層構造を破壊（ショート不良）する虞があって好ましくなく、平均粒径が０．４μｍを超えるとピンニング効果が低下する虞があって好ましくない。 In order to exhibit the pinning effect in the ceramic powder A, it is preferable that the average particle size of the ceramic powder A is small. However, if the average particle size is less than 0.2 μm, the ceramic powder is agglomerated and the dispersibility is remarkably lowered. The structure may be destroyed (short circuit failure), which is not preferable. If the average particle size exceeds 0.4 μm, the pinning effect may be deteriorated.
セラミック粉末Ｂは、平均粒径が０．６〜０．８μｍである。セラミック粉末Ｂは、ニッケル粉末の平均粒径（０．２〜１．０μｍ）に比較的近いため、焼成時に内部電極層中でセラミック層との共材である上下のセラミック粉末粒子同士が焼結して比較的容易に柱構造を形成し、上下のセラミック層を接続して内部電極とセラミック層間の密着力を向上させることができる。 The ceramic powder B has an average particle size of 0.6 to 0.8 μm. Since the ceramic powder B is relatively close to the average particle diameter (0.2 to 1.0 μm) of the nickel powder, the upper and lower ceramic powder particles, which are co-materials with the ceramic layer, are sintered in the internal electrode layer during firing. Thus, the column structure can be formed relatively easily, and the upper and lower ceramic layers can be connected to improve the adhesion between the internal electrode and the ceramic layer.
従って、焼成時の最高温度以降の降温段階で内部電極層及びセラミック層が焼結して流動性が低下し、内部電極層とセラミック層の熱膨張率の差によって両者間に内部応力が作用しても、焼成時に内部電極中で形成される共材の柱構造によって内部電極層とセラミック層と間の密着力が向上するため、降温段階における内部応力によるボイドやクラックの発生を抑制し、延いてはデラミネーションを抑制することができる。 Therefore, the internal electrode layer and the ceramic layer are sintered at the temperature lowering stage after the maximum temperature during firing, the fluidity is lowered, and internal stress acts between the two due to the difference in thermal expansion coefficient between the internal electrode layer and the ceramic layer. However, the cohesive columnar structure formed in the internal electrode during firing improves the adhesion between the internal electrode layer and the ceramic layer. In this case, delamination can be suppressed.
内部電極中でセラミック粉末Ｂによって柱構造を形成するためには、セラミック粉末Ｂの平均粒径はニッケル粉末と近い方が好ましいが、平均粒径が０．６μｍ未満ではニッケル粉末の平均粒径との差が大きく柱構造を形成し難くなって好ましくない。また、平均粒径が０．８μｍを超えると１．０μｍ以下の薄層化した内部電極層に適さないと共に積層構造を破壊（ショート不良）する虞があって好ましくない。 In order to form a column structure with the ceramic powder B in the internal electrode, the average particle size of the ceramic powder B is preferably close to that of the nickel powder, but if the average particle size is less than 0.6 μm, the average particle size of the nickel powder is This is not preferable because the difference between the two is large and it is difficult to form a column structure. An average particle size exceeding 0.8 μm is not preferable because it is not suitable for a thinned internal electrode layer having a thickness of 1.0 μm or less, and the laminated structure may be destroyed (short circuit failure).
また、本発明ではセラミック粉末全量に対するセラミック粉末Ａの重量比（Ａ／（Ａ＋Ｂ））を０．３〜０．７に設定する。セラミック粉末Ａの重量比が０．３未満ではピンニング効果が発現し難くなって好ましくなく、その重量比が０．７を超えるとセラミック粉末Ｂによって柱構造を形成し難くなって好ましくない。つまり、セラミック粉末Ａの重量比が上記範囲を逸脱すると焼成時の昇温段階及び降温段階のいずれかの段階で内部電極層とセラミック層との間でデラミネーションやクラックを発生する虞があって好ましくない。 In the present invention, the weight ratio (A / (A + B)) of the ceramic powder A to the total amount of the ceramic powder is set to 0.3 to 0.7. If the weight ratio of the ceramic powder A is less than 0.3, the pinning effect is hardly exhibited, which is not preferable. If the weight ratio exceeds 0.7, it is difficult to form a column structure with the ceramic powder B. In other words, if the weight ratio of the ceramic powder A deviates from the above range, delamination or cracks may occur between the internal electrode layer and the ceramic layer at any of the temperature rising stage and the temperature falling stage during firing. It is not preferable.
本発明の積層セラミック電子部品は、上記導電性ペーストを用いて内部電極を形成したものである。上記導電性ペーストを用いて積層セラミック電子部品の内部電極を形成するため、デラミネーションやクラックの構造欠陥を抑制することができ、しかも内部電極層とセラミック層の積層構造の破壊によるショート不良を防止することができ、信頼性の高い積層セラミックコンデンサ等の積層セラミック電子部品を得ることができる。本発明は、内部電極を有する積層セラミック電子部品に広く適用することができ、例えば積層セラミックコンデンサに好ましく適用することができる。 The multilayer ceramic electronic component of the present invention is one in which an internal electrode is formed using the conductive paste. The internal electrode of multilayer ceramic electronic parts is formed using the above conductive paste, so that structural defects such as delamination and cracks can be suppressed, and short circuit failure due to the breakdown of the multilayer structure of internal electrode layer and ceramic layer can be prevented. Therefore, it is possible to obtain a multilayer ceramic electronic component such as a multilayer ceramic capacitor with high reliability. The present invention can be widely applied to multilayer ceramic electronic components having internal electrodes, and can be preferably applied to, for example, multilayer ceramic capacitors.
本発明によれば、積層セラミック電子部品を形成するセラミック層と１．０μｍ以下の厚さを有する内部電極層間のクラックやデラミネーション等の構造欠陥を防止すると共に内部電極とセラミック層の積層構造の破壊によるショート不良を防止することができる内部電極用導電性ペースト及び積層セラミック電子部品を提供することができる。
According to the onset bright, layered structure of the internal electrodes and the ceramic layers while preventing structural defects such as cracks and delamination of the internal electrode layers having a ceramic layer and 1.0μm or less in thickness to form a multilayer ceramic electronic component Thus, it is possible to provide a conductive paste for internal electrodes and a multilayer ceramic electronic component that can prevent a short-circuit failure due to breakage .
以下、本発明の導電性ペースト及び積層セラミック電子部品の好適な実施例について説明する。本実施例では積層セラミック電子部品として積層セラミックコンデンサを作製し、積層セラミックコンデンサの積層断面を観察すると共に電気的特性試験を行ってその特性を評価した。 Hereinafter, preferred embodiments of the conductive paste and the multilayer ceramic electronic component of the present invention will be described. In this example, a multilayer ceramic capacitor was produced as a multilayer ceramic electronic component, the multilayer cross section of the multilayer ceramic capacitor was observed, and an electrical characteristic test was performed to evaluate the characteristics.
（１）導電性ペーストの調製
まず、ジヒドロターピニルアセテート９４重量部に、エチルセルロース樹脂６重量部を徐々に加えて、攪拌機によって２４時間攪拌して有機ビヒクルを調製した。この有機ビヒクル１３重量部に、表１に示す試料Ｎｏ.１〜１２の共材であるセラミック粉末を５重量部、希釈溶剤として使用するアセトン、ステアリン酸、オイゲノールを２５０重量部混合して、容量０．６Ｌのサンドミルによって共材を２時間分散させた。その後、ニッケル粉末４２重量部、オイゲノール１重量部、ビヒクル３０重量部及びジヒドロターピニルアセテート１０重量部を混合して、容量０．６Ｌのサンドミルによって１時間分散させてセラミック粉末とニッケル粉末を均一に分散させた後、減圧装置付きプラネタリミキサでアセトンを蒸発させて表１に示す試料Ｎｏ.１〜１２の導電性ペーストを得た。表１において、試料Ｎｏ.１〜７が本実施例の導電性ペーストであり、試料Ｎｏ.８〜１２が比較例の導電性ペーストである。
(1) Preparation of conductive paste First, 6 parts by weight of ethyl cellulose resin was gradually added to 94 parts by weight of dihydroterpinyl acetate, and stirred for 24 hours with a stirrer to prepare an organic vehicle. Mixing 13 parts by weight of this organic vehicle with 5 parts by weight of ceramic powder which is a co-material of sample Nos. 1 to 12 shown in Table 1, and 250 parts by weight of acetone, stearic acid and eugenol used as a diluent solvent, The common material was dispersed for 2 hours by a 0.6 L sand mill. Thereafter, 42 parts by weight of nickel powder, 1 part by weight of eugenol, 30 parts by weight of vehicle and 10 parts by weight of dihydroterpinyl acetate are mixed and dispersed by a sand mill having a capacity of 0.6 L for 1 hour to make the ceramic powder and nickel powder uniform. Then, acetone was evaporated with a planetary mixer with a decompression device to obtain conductive pastes of sample Nos. 1 to 12 shown in Table 1. In Table 1, sample Nos. 1 to 7 are conductive pastes of this example, and sample Nos. 8 to 12 are conductive pastes of comparative examples.
（２）積層セラミックコンデンサの作製
ポリビニルブチラール樹脂１０重量部、チタン酸バリウム５０重量部及びエタノール、トルエンを混合した後、この混合物をサンドミルによって３時間粉砕、混合してセラミックスラリーを得た。次いで、このセラミックスラリーをドクターブレード法によってフィルム上に塗布してセラミックグリーンシートを形成した。その後、セラミックグリーンシート上に試料Ｎｏ.１の導電性ペーストを印刷し、このセラミックグリーンシートを複数枚作製した。次いで、導電性ペーストが印刷されたセラミックグリーンシートをそれぞれ所定枚数ずつ積層し、所定の圧力で圧着して積層体を得た。更に、これらの積層体を切断して所定の寸法のチップを作製した後、これらのチップを窒素／水素雰囲気中、９００〜１３００℃の温度で１０時間焼成してコンデンサ素体を得た。試料Ｎｏ.２〜１２の導電性ペーストについてもそれぞれ同様の手順でコンデンサ素体を作製した。
(2) Production of Multilayer Ceramic Capacitor After mixing 10 parts by weight of polyvinyl butyral resin, 50 parts by weight of barium titanate, ethanol and toluene, this mixture was pulverized and mixed by a sand mill for 3 hours to obtain a ceramic slurry. Next, this ceramic slurry was applied onto a film by a doctor blade method to form a ceramic green sheet. Then, the conductive paste of sample No. 1 was printed on the ceramic green sheet, and a plurality of ceramic green sheets were produced. Next, a predetermined number of ceramic green sheets each having a conductive paste printed thereon were stacked and pressed with a predetermined pressure to obtain a stacked body. Furthermore, after cutting these laminated bodies to produce chips having a predetermined size, these chips were fired in a nitrogen / hydrogen atmosphere at a temperature of 900 to 1300 ° C. for 10 hours to obtain capacitor bodies. Capacitor bodies were produced in the same manner for the conductive pastes of Sample Nos. 2 to 12, respectively.
（３）積層セラミックコンデンサの観察及び電気的特性試験
顕微鏡を用いて試料Ｎｏ.１〜１２のコンデンサ素体の断面のクラック発生数を観察し、その結果を表１の「積層コンデンサクラック」の欄に示した。また、各コンデンサ素体について外部電極間の絶縁性試験を行い、それぞれの結果を表１の「積層コンデンサショート不良」の欄に示した。これらの観察及び試験はそれぞれ１０００個の試料について行った。
(3) Observation of multilayer ceramic capacitor and electrical characteristic test Using a microscope, the number of cracks in the cross section of the capacitor body of sample Nos. 1 to 12 was observed, and the result is shown in the column of “Multilayer capacitor crack” in Table 1. It was shown to. Each capacitor element was subjected to an insulation test between external electrodes, and the results are shown in the column of “Multilayer capacitor short defect” in Table 1. Each of these observations and tests was performed on 1000 samples.
表１に示す結果によれば、共材であるセラミック粉末Ａ及びセラミック粉末Ｂそれぞれの平均粒径及びセラミック粉末Ａの重量比（Ａ／（Ａ＋Ｂ））が本発明の範囲内にある試料Ｎｏ.１〜７のコンデンサ素体は、いずれもクラックが観察されず、また積層構造の破壊に基づくショート不良もないことが判った。 According to the results shown in Table 1, the average particle diameters of the ceramic powder A and the ceramic powder B, which are co-materials, and the weight ratio (A / (A + B)) of the ceramic powder A are within the scope of the present invention. It was found that no cracks were observed in any of the capacitor bodies 1 to 7 and there was no short circuit failure due to the destruction of the laminated structure.
これに対して、平均粒径が本発明の範囲より小さい０．１３μｍのセラミック粉末Ａを共材として含む試料Ｎｏ.１０は、他の要件が本発明の範囲内にあっても、１０００個のコンデンサ素体中、７個にクラックが観察され、３７個にショート不良があった。 On the other hand, Sample No. 10 containing 0.13 μm ceramic powder A having an average particle size smaller than the range of the present invention as a co-material is 1000 pieces even if other requirements are within the range of the present invention. In the capacitor body, 7 cracks were observed and 37 short-circuit defects.
平均粒径が本発明の範囲より大きい０.９２μｍのセラミック粉末Ａを含む試料Ｎｏ.１２は、他の要件が本発明の範囲内にあっても、１０００個のコンデンサ素体中、２８個にショート不良があった。この場合にはいずれのコンデンサ素体にもクラックは観察されなかった。 Sample No. 12 containing ceramic powder A having an average particle size of 0.92 μm larger than the range of the present invention is 28 in 1000 capacitor bodies, even if other requirements are within the range of the present invention. There was a short circuit. In this case, no crack was observed in any of the capacitor bodies.
セラミック粉末Ａの重量比が本発明の範囲（Ａ／（Ａ＋Ｂ））＝０．３〜０．７より小さい試料Ｎｏ.８は、その他の要件が本発明の範囲内にあっても、１０００個のコンデンサ素体中、１２個にクラックが観察された。また、セラミック粉末Ａの重量比が本発明の範囲より大きい試料Ｎｏ.９は、その他の要件が本発明の範囲内にあっても、１０００個のコンデンサ素体中、２５個にクラックが観察された。この場合にもいずれのコンデンサ素体にもクラックは観察されなかった。 Sample No. 8 in which the weight ratio of the ceramic powder A is smaller than the range of the present invention (A / (A + B)) = 0.3 to 0.7 is 1000 pieces even if other requirements are within the range of the present invention. Cracks were observed in 12 of the capacitor body. Further, in sample No. 9 in which the weight ratio of the ceramic powder A is larger than the range of the present invention, even if other requirements are within the range of the present invention, 25 cracks are observed in 1000 capacitor bodies. It was. Also in this case, no crack was observed in any of the capacitor bodies.
更に、共材としてセラミック粉末Ａのみを含む試料Ｎｏ.１１は、１０００個のコンデンサ素体中、１２個にクラックが観察されたが、ショート不良はなかった。 Furthermore, in sample No. 11 containing only ceramic powder A as a co-material, cracks were observed in 12 of 1000 capacitor bodies, but there was no short circuit defect.
以上説明したように本実施例によれば、セラミック粉末は、平均粒径が０．２〜０．４μｍであるセラミック粉末Ａと、平均粒径が０．６〜０．８μｍであるセラミック粉末Ｂと含有し、且つ、セラミック粉末全量に対するセラミック粉末Ａの重量比（Ａ／（Ａ＋Ｂ））が０．３〜０．７である導電性ペーストを用いて積層セラミックコンデンサを作製することによって、クラックの発生を防止することができると共に積層構造の破壊に基づくショート不良を防止することができ、信頼性の高い積層セラミックコンデンサを得ることができる。 As described above, according to the present example, the ceramic powder includes ceramic powder A having an average particle diameter of 0.2 to 0.4 μm and ceramic powder B having an average particle diameter of 0.6 to 0.8 μm. And a multilayer ceramic capacitor using a conductive paste in which the weight ratio of ceramic powder A to the total amount of ceramic powder (A / (A + B)) is 0.3 to 0.7. Generation | occurrence | production can be prevented and the short circuit failure based on destruction of a laminated structure can be prevented, and a highly reliable laminated ceramic capacitor can be obtained.
尚、本発明は上記実施例に何ら制限されるものではなく、導電性ペーストに含まれるセラミック粉末が平均粒径の異なるセラミック粉末Ａ及びセラミック粉末Ｂを含み、セラミック粉末Ａの平均粒径が０．２〜０．４μｍであり、セラミック粉末Ｂの平均粒径が０．６〜０．８μｍであり、しかもセラミック粉末Ａの重量比（Ａ／（Ａ＋Ｂ））が０．３〜０．７の範囲にあるものであれば、全て本発明に包含される。 In addition, this invention is not restrict | limited at all to the said Example, The ceramic powder contained in an electrically conductive paste contains the ceramic powder A and the ceramic powder B from which average particle diameter differs, and the average particle diameter of the ceramic powder A is 0. The average particle size of the ceramic powder B is 0.6 to 0.8 μm, and the weight ratio (A / (A + B)) of the ceramic powder A is 0.3 to 0.7. Anything within the scope is included in the present invention.
本発明の導電性ペーストは、積層セラミックコンデンサ等の積層セラミック電子部品を製造する場合に好適に用いることができる。 The electrically conductive paste of this invention can be used suitably when manufacturing multilayer ceramic electronic components, such as a multilayer ceramic capacitor.
Claims (2)
前記内部電極用導電性ペーストは、ニッケル粉末と、有機ビヒクルと、前記セラミック層と同一種またはた類似の組成からなるセラミック粉末と、を含有し、
前記ニッケル粉末は、平均粒径が０．２〜１．０μｍであり、
前記セラミック粉末は、平均粒径が０．２〜０．４μｍであるセラミック粉末Ａと、平均粒径が０．６〜０．８μｍであるセラミック粉末Ｂと、を含有し、且つ、前記セラミック粉末全量に対する前記セラミック粉末Ａの重量比（Ａ／（Ａ＋Ｂ））が０．３〜０．７であり、
１．０μｍ以下の厚さの未焼成の内部電極として形成されることを特徴とする内部電極用導電性ペースト。 A conductive paste for internal electrodes used for the internal electrodes constituting a multilayer ceramic electronic component having a laminate composed of a plurality of ceramic layers, and internal electrodes formed between the ceramic layers,
The conductive paste for internal electrodes contains a nickel powder, an organic vehicle, and ceramic powder consisting of the ceramic layer and the similar composition the same species or was, a,
The nickel powder has an average particle size of 0.2 to 1.0 μm,
The ceramic powder contains ceramic powder A having an average particle diameter of 0.2 to 0.4 μm and ceramic powder B having an average particle diameter of 0.6 to 0.8 μm, and the ceramic powder The weight ratio (A / (A + B)) of the ceramic powder A to the total amount is 0.3 to 0.7,
1.0μm or less of the thickness of the green internal electrode conductive paste is formed as an internal electrode, characterized in Rukoto of.
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