JP2011256091A - Dielectric ceramic and laminated ceramic capacitor using the same - Google Patents
Dielectric ceramic and laminated ceramic capacitor using the same Download PDFInfo
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本発明は誘電体セラミックおよびそれを用いたコンデンサに関し、詳しくは、ＢａＴｉＯ3系の誘電体セラミックおよびそれを誘電体層の構成材料として用いた積層セラミックコンデンサに関する。 The present invention relates to a dielectric ceramic and a capacitor using the dielectric ceramic, and more particularly to a BaTiO 3 based dielectric ceramic and a multilayer ceramic capacitor using the dielectric ceramic as a constituent material of the dielectric layer.
近年、電子機器の小型・軽量化にともない、小型で、大容量を取得することが可能な積層セラミックコンデンサが広く用いられている。この積層セラミックコンデンサは、例えば、図１に示すように、セラミック積層体（積層セラミック素子）１０の内部に配設された内部電極１２が、誘電体層であるセラミック層（誘電体セラミック層）１１を介して積層され、かつ、セラミック積層体１０の両端面には、交互に逆側の端面に露出した内部電極１２と導通するように一対の外部電極１３ａ，１３ｂが配設された構造を有している。 In recent years, with the reduction in size and weight of electronic devices, multilayer ceramic capacitors that are small in size and capable of acquiring a large capacity are widely used. For example, as shown in FIG. 1, the multilayer ceramic capacitor has a ceramic layer (dielectric ceramic layer) 11 in which an internal electrode 12 disposed in a ceramic multilayer body (multilayer ceramic element) 10 is a dielectric layer. And a pair of external electrodes 13a and 13b are disposed on both end faces of the ceramic laminate 10 so as to be electrically connected to the internal electrodes 12 exposed on the opposite end faces. is doing.
そして、このような積層セラミックコンデンサにおいては、誘電体層として、 高い誘電率を有するＢａＴｉＯ3系セラミック材料が一般的に用いられている。 In such a multilayer ceramic capacitor, a BaTiO 3 ceramic material having a high dielectric constant is generally used as the dielectric layer.
さらに、ＢａＴｉＯ3系セラミック材料として、温度特性や絶縁性、信頼性（寿命特性）などの特性を向上させる目的で、種々の副成分、例えば、希土類元素やＭｇなどを添加したものが用いられている。 Furthermore, as a BaTiO 3 ceramic material, materials added with various subcomponents such as rare earth elements and Mg are used for the purpose of improving characteristics such as temperature characteristics, insulating properties, and reliability (life characteristics). Yes.
また、ＢａＴｉＯ3系セラミック材料の温度特性や信頼性（寿命特性）を制御可能に保ちつつ、両立させるために、セラミック粒子（結晶粒子）の表層部に副成分が固溶し、結晶粒子の内部には殆ど副成分が固溶していない、いわゆるコア・シェル構造とよばれる結晶構造とすることも行われている。 Further, in order to achieve both controllability and controllability of temperature characteristics and reliability (life characteristics) of the BaTiO 3 ceramic material, subcomponents are dissolved in the surface layer portion of the ceramic particles (crystal particles), and the inside of the crystal particles In other cases, a crystal structure called a so-called core-shell structure in which almost no subcomponents are dissolved is also used.
たとえば、特許文献１には、誘電体層が、コア部とコア部を囲繞するシェル部とからなるセラミック粒子の焼結体から構成されているとともに、セラミック粒子のシェル部にはＭｎ，Ｖ，Ｃｒ，Ｃｏ，Ｆｅ，Ｎｉ，ＣｕおよびＭｏから選択された１種又は２種以上のアクセプタ型元素、Ｍｇおよび希土類元素（Ｈｏ，Ｓｃ，Ｙ，Ｇｄ，Ｄｙ，Ｅｒ，Ｙｂ，Ｔｂ，Ｔｍ，Ｌｕ）が含まれており、シェル部に含まれている上記アクセプタ型元素の濃度がコア・シェル境界から粒界側に向かって高くなるようにした積層セラミックコンデンサが提案されている（特許文献１参照）。 For example, in Patent Document 1, the dielectric layer is composed of a sintered body of ceramic particles including a core portion and a shell portion surrounding the core portion, and Mn, V, One or more acceptor elements selected from Cr, Co, Fe, Ni, Cu and Mo, Mg and rare earth elements (Ho, Sc, Y, Gd, Dy, Er, Yb, Tb, Tm, Lu And a multilayer ceramic capacitor in which the concentration of the acceptor element contained in the shell portion is increased from the core / shell boundary toward the grain boundary side is proposed (see Patent Document 1). ).
しかしながら、誘電体層に特許文献１に示されているようなセラミック誘電体を用いた積層セラミックコンデンサの場合、例えば、高温や高電界強度の環境下で使用すると、信頼性（寿命特性）が低下するという問題点がある。そのため、さらに寿命特性に優れた積層セラミックコンデンサを構成することが可能な誘電体材料の開発が望まれているのが実情である。 However, in the case of a multilayer ceramic capacitor using a ceramic dielectric as disclosed in Patent Document 1 as a dielectric layer, for example, when used in an environment of high temperature or high electric field strength, reliability (life characteristics) is reduced. There is a problem of doing. For this reason, there is a demand for development of a dielectric material capable of forming a multilayer ceramic capacitor having further excellent life characteristics.
本発明は、上記課題を解決するものであり、積層セラミックコンデンサの誘電体層として用いた場合に、容量温度特性が良好で、かつ、寿命特性に優れた積層セラミックコンデンサを得ることが可能な誘電体セラミック、およびそれを用いて誘電体層を形成した信頼性（寿命特性）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 solves the above-mentioned problems, and when used as a dielectric layer of a multilayer ceramic capacitor, the dielectric temperature capable of obtaining a multilayer ceramic capacitor having good capacitance-temperature characteristics and excellent life characteristics. It is an object of the present invention to provide a body ceramic and a multilayer ceramic capacitor excellent in reliability (life characteristics) in which a dielectric layer is formed using the body ceramic.
上記課題を解決するため、本発明の誘電体セラミックは、
ＢａＴｉＯ3系セラミック粒子を主相粒子とする焼結体からなり、
前記ＢａＴｉＯ3系セラミック粒子は、表層部であるシェル部と、シェル部の内側のコア部とを備え、
副成分として、Ｒ（Ｒは、希土類元素であって、Ｎｄ，Ｓｍ，Ｅｕ，Ｇｄ，Ｔｂ，Ｄｙ，Ｈｏ，ＥｒおよびＹからなる群より選ばれる少なくとも１種）、および、Ｍ（Ｍは、Ｍｇ，Ｍｎ，Ｎｉ，Ｃｏ，Ｆｅ，Ｃｒ，Ｃｕ，Ａｌ，Ｍｏ，ＷおよびＶからなる群より選ばれる少なくとも１種）を含み、
前記ＢａＴｉＯ3系セラミック粒子の前記シェル部が、前記Ｒおよび前記Ｍを含むとともに、前記Ｒおよび前記Ｍの合計濃度は、粒界から前記コア部に向かって勾配を有し、かつ、極小となる部分と、極大となる部分とを有していること
を特徴としている。
In order to solve the above problems, the dielectric ceramic of the present invention is
It consists of a sintered body with BaTiO 3 ceramic particles as main phase particles,
The BaTiO 3 based ceramic particles include a shell portion that is a surface layer portion and a core portion inside the shell portion,
As subcomponents, R (R is a rare earth element and is at least one selected from the group consisting of Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, and Y), and M (M is Mg, Mn, Ni, Co, Fe, Cr, Cu, Al, Mo, W, and V).
The shell portion of the BaTiO 3 based ceramic particles includes the R and the M, and the total concentration of the R and the M has a gradient from the grain boundary toward the core portion, and is minimal. It is characterized by having a part and a part that becomes maximum.
本発明の誘電体セラミックにおいては、前記Ｒおよび前記Ｍの合計濃度が極小となる部分および極大となる部分の、少なくとも一方を２つ以上有していてもよい。 The dielectric ceramic of the present invention may have two or more of at least one of a portion where the total concentration of R and M is minimized and a portion where the total concentration is maximized.
また、前記Ｒおよび前記Ｍの合計濃度が極大となる部分の値である極大値は、粒界における前記Ｒおよび前記Ｍの合計濃度の値よりも小さいことが望ましい。 Moreover, it is desirable that the maximum value, which is the value at the portion where the total concentration of R and M becomes maximum, is smaller than the value of the total concentration of R and M at the grain boundary.
また、前記ＢａＴｉＯ3系セラミック粒子において、Ｂａの一部がＣａおよび／またはＳｒで置換されていてもよく、Ｔｉの一部がＺｒおよび／またはＨｆで置換されていてもよい。
すなわち、Ｂａの一部がＣａおよび／またはＳｒで置換され、かつ、Ｔｉの一部がＺｒおよび／またはＨｆで置換されていてもよく、また、ＢａとＴｉのいずれか一方だけが上述の成分で置換されていてもよい。
In the BaTiO 3 ceramic particles, a part of Ba may be substituted with Ca and / or Sr, and a part of Ti may be substituted with Zr and / or Hf.
That is, a part of Ba may be substituted with Ca and / or Sr, and a part of Ti may be substituted with Zr and / or Hf, and only one of Ba and Ti is the above-described component. May be substituted.
本発明の積層セラミックコンデンサは、
複数の誘電体層と複数の内部電極とが一体的に積層された構造を有する積層セラミックコンデンサであって、
前記誘電体層が、本発明にかかる誘電体セラミックから形成されていること
を特徴としている。
The multilayer ceramic capacitor of the present invention is
A multilayer ceramic capacitor having a structure in which a plurality of dielectric layers and a plurality of internal electrodes are integrally laminated,
The dielectric layer is formed of a dielectric ceramic according to the present invention.
本発明の誘電体セラミックは、ＢａＴｉＯ3系セラミック粒子を主相粒子とする焼結体からなり、ＢａＴｉＯ3系セラミック粒子は、シェル部とコア部とを備え、副成分として、Ｒ（Ｒは、希土類元素であって、Ｎｄ，Ｓｍ，Ｅｕ，Ｇｄ，Ｔｂ，Ｄｙ，Ｈｏ，ＥｒおよびＹからなる群より選ばれる少なくとも１種）、および、Ｍ（Ｍは、Ｍｇ，Ｍｎ，Ｎｉ，Ｃｏ，Ｆｅ，Ｃｒ，Ｃｕ，Ａｌ，Ｍｏ，ＷおよびＶからなる群より選ばれる少なくとも１種）を含み、ＲおよびＭが、ＢａＴｉＯ3系セラミック粒子のシェル部に存在するとともに、ＲおよびＭの合計濃度は、粒界からコア部に向かって勾配を有し、かつ、極小となる部分と、極大となる部分とを有するように構成されているので、温度特性や絶縁性、信頼性（寿命特性）などに優れた誘電体セラミックを得ることが可能になる。そして、本発明の誘電体セラミックを用いて誘電体層を形成することにより、容量温度特性に優れ、高温や高電界強度の環境下でも、良好な信頼性（寿命特性）を有する積層セラミックコンデンサを得ることができる。
なお、このような作用効果が得られるのは、ＲおよびＭの合計濃度が、粒界からコア部に向かって勾配を有し、かつ、極小となる部分と、極大となる部分とを有することで、キャリアとなる導電電子や酸素空孔などの移動を抑制できることによる。
The dielectric ceramic of the present invention is composed of a sintered body having BaTiO 3 ceramic particles as main phase particles, and the BaTiO 3 ceramic particles include a shell portion and a core portion, and R (R is A rare earth element, at least one selected from the group consisting of Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er and Y, and M (M is Mg, Mn, Ni, Co, Fe) , Cr, Cu, Al, Mo, W and V), and R and M are present in the shell portion of the BaTiO 3 ceramic particles, and the total concentration of R and M is Since it has a gradient from the grain boundary toward the core and has a minimum part and a maximum part, temperature characteristics, insulation properties, reliability (life characteristics), etc. Excellent invitation to It is possible to obtain a body ceramic. Then, by forming a dielectric layer using the dielectric ceramic of the present invention, a multilayer ceramic capacitor having excellent capacitance temperature characteristics and good reliability (lifetime characteristics) even in an environment of high temperature and high electric field strength. Obtainable.
In addition, such an effect is obtained because the total concentration of R and M has a gradient from the grain boundary toward the core, and has a minimum portion and a maximum portion. Thus, the movement of conductive electrons or oxygen vacancies as carriers can be suppressed.
また、本発明の誘電体セラミックにおいて、上述の極小となる部分および極大となる部分は、１つである場合に限らず、少なくとも一方を２つ以上有していてもよく、その場合にも、温度特性や絶縁性、寿命特性などに優れた誘電体セラミックが得られ、この誘電体セラミックを誘電体層として用いることにより、容量温度特性に優れ、高温や高電界強度の環境下でも、良好な寿命特性を有する積層セラミックコンデンサを得ることができる。 Further, in the dielectric ceramic of the present invention, the minimum portion and the maximum portion described above are not limited to one, and may have at least one of two or more. Dielectric ceramics with excellent temperature characteristics, insulation properties, life characteristics, etc. can be obtained, and by using this dielectric ceramic as a dielectric layer, it has excellent capacity-temperature characteristics and is good even in high temperature and high electric field strength environments. A multilayer ceramic capacitor having life characteristics can be obtained.
また、ＲおよびＭの合計濃度の極大値を、粒界におけるＲおよびＭの合計濃度の値よりも小さくなるようにした場合、良好なバイアス特性を得る（ＤＣ電圧を印加したときの静電容量の変化率を小さくする）ことが可能になり好ましい。 Further, when the maximum value of the total concentration of R and M is made smaller than the value of the total concentration of R and M at the grain boundary, good bias characteristics are obtained (capacitance when a DC voltage is applied). It is possible to reduce the rate of change of
また、本発明において、ＢａＴｉＯ3系セラミック粒子のＢａの一部をＣａおよび／またはＳｒで置換したり、Ｔｉの一部をＺｒおよび／またはＨｆで置換したりすることにより、特性を制御して、所望の特性を備えた誘電体セラミックを得ることが可能になる。 In the present invention, the BaTiO 3 ceramic particles may be partially replaced with Ca and / or Sr, or Ti may be replaced with Zr and / or Hf to control the characteristics. Thus, it becomes possible to obtain a dielectric ceramic having desired characteristics.
本発明の積層セラミックコンデンサは、誘電体層が、本発明の誘電体セラミックから形成されているので、高温や高電界強度の環境のもとでも、良好な寿命特性を実現することができる。 In the multilayer ceramic capacitor of the present invention, since the dielectric layer is formed of the dielectric ceramic of the present invention, good life characteristics can be realized even under high temperature and high electric field strength environments.
以下に本発明の実施例を示して、本発明の特徴とするところをさらに詳しく説明する。 Examples of the present invention will be described below to describe the features of the present invention in more detail.
(Ａ)誘電体セラミック原料の作製
まず、出発原料として主成分原料であるＢａＴｉＯ3粉末を準備した。
なお、主成分原料であるＢａＴｉＯ3粉末は、その製造方法に特別の制約はなく、固相合成法、水熱合成法、加水分解法など、公知の種々の方法で作製されたものを使用することが可能である。さらに、ＢａＴｉＯ3を作製する際に用いる素材や、添加成分の化合物形態は、酸化物、炭酸物に限らず、塩化物、金属有機化合物など種々の形態のものを用いることができる。
(A) Production of Dielectric Ceramic Raw Material First, BaTiO 3 powder as a main component raw material was prepared as a starting raw material.
The BaTiO 3 powder, which is the main component raw material, is not particularly limited in its production method, and those produced by various known methods such as a solid phase synthesis method, a hydrothermal synthesis method, and a hydrolysis method are used. It is possible. Furthermore, the raw materials used when producing BaTiO 3 and the compound forms of the additive components are not limited to oxides and carbonates, and various forms such as chlorides and metal organic compounds can be used.
それから、このＢａＴｉＯ3粉末に対し、表１に記載のＭ成分の酸化物粉末を添加し、純水を媒体として、ボールミルにより１２時間混合した後、乾燥することにより混合粉末を得た。 Then, the M component oxide powders listed in Table 1 were added to the BaTiO 3 powder, mixed for 12 hours by a ball mill using pure water as a medium, and then dried to obtain a mixed powder.
この混合粉末を１０００℃で仮焼することにより仮焼体（組成物）を得た。そして、この仮焼体（組成物）を１次粒子にまで解砕することにより、仮焼済みの原料粉末を得た。 The mixed powder was calcined at 1000 ° C. to obtain a calcined body (composition). And the calcined raw material powder was obtained by crushing this calcined body (composition) to primary particles.
次に、得られた仮焼済みの原料粉末に、表１に記載のＲ成分の酸化物粉末およびガラス成分であるＳｉＯ2を配合した。なお、表１におけるＲ成分、Ｍ成分、ガラス成分のｍｏｌ部は、主成分（ＢａＴｉＯ3系粉末）１００ｍｏｌ部に対する割合である。 Next, the obtained calcined raw material powder was blended with the R component oxide powder and the glass component SiO 2 shown in Table 1. In Table 1, the mol parts of the R component, M component, and glass component are ratios relative to 100 mol parts of the main component (BaTiO 3 -based powder).
それから、上述のようにＳｉＯ2を配合した原料粉末に対し、アンモニア水を０．２ｗｔ％添加し、水を媒体として、ボールミルにより２４時間混合することにより、原料粉末粒子の表面改質処理を行った。 Then, 0.2 wt% of ammonia water is added to the raw material powder blended with SiO 2 as described above, and the raw powder particles are subjected to surface modification treatment by mixing with water as a medium by a ball mill for 24 hours. It was.
次に、２４時間混合して表面改質処理を行った後のスラリーを蒸発乾燥し、４００℃で熱処理して残留アンモニウムを除去することにより、表１の試料番号１〜１９の誘電体配合原料粉末を得た。 Next, the slurry after the surface modification treatment by mixing for 24 hours is evaporated to dryness, and the residual ammonium is removed by heat treatment at 400 ° C. A powder was obtained.
なお、この誘電体配合原料粉末において、Ｍ成分、Ｒ成分、およびガラス成分（ＳｉＯ2）は、通常、主成分原料であるＢａＴｉＯ3粉末１００ｍｏｌ部に対して、以下の範囲で配合することが望ましい。
Ｍ成分 ：０．２〜４．０ｍｏｌ部
Ｒ成分 ：０．１〜４．０ｍｏｌ部
ガラス成分：０．０５〜３．０ｍｏｌ部
In this dielectric compounding raw material powder, it is desirable that the M component, R component, and glass component (SiO 2 ) are usually blended in the following range with respect to 100 mol parts of BaTiO 3 powder as the main component raw material. .
M component: 0.2-4.0 mol part R component: 0.1-4.0 mol part Glass component: 0.05-3.0 mol part
また、表１の試料番号２０の誘電体配合原料粉末は、ＢａＴｉＯ3粉末に、Ｒ成分の酸化物粉末、Ｍ成分の酸化物粉末およびＳｉＯ2粉末を配合し、アンモニア水を添加することなく、純水を媒体として、ボールミルにて混合した後、乾燥することにより得た、比較例としての誘電体配合原料粉末である。なお、この試料番号２０の誘電体配合原料粉末については、特に熱処理も行わなかった。 In addition, the dielectric compounding raw material powder of Sample No. 20 in Table 1 is compounded with the BaTiO 3 powder, the R component oxide powder, the M component oxide powder and the SiO 2 powder, without adding ammonia water, This is a dielectric compound raw material powder as a comparative example obtained by mixing with a ball mill using pure water as a medium and then drying. The dielectric compound raw material powder of Sample No. 20 was not particularly heat treated.
(Ｂ)積層セラミックコンデンサの作製
上記(Ａ)で作製した、表１の試料番号１〜２０の誘電体セラミック原料に、ポリビニルブチラール系バインダーおよび有機溶媒（この実施例１ではエタノール）を加えて、ボールミルにより所定の時間、湿式混合し、セラミックスラリーを作製した。
(B) Production of Multilayer Ceramic Capacitor A polyvinyl butyral binder and an organic solvent (ethanol in this Example 1) were added to the dielectric ceramic raw materials of sample numbers 1 to 20 in Table 1 produced in (A) above. Wet mixing was performed for a predetermined time with a ball mill to produce a ceramic slurry.
このセラミックスラリーをドクターブレード法によりシート成形し、矩形で、焼成後の誘電体セラミック層厚が１μｍになるようなセラミックグリーンシートを作製した。 This ceramic slurry was formed into a sheet by a doctor blade method to produce a ceramic green sheet having a rectangular shape and a dielectric ceramic layer thickness of 1 μm after firing.
次に、上記セラミックグリーンシート上に、ニッケル粉末を導電成分とする導電ペーストをスクリーン印刷し、焼成後に内部電極となる導電ペースト層（内部電極パターン）を形成した。 Next, a conductive paste containing nickel powder as a conductive component was screen-printed on the ceramic green sheet to form a conductive paste layer (internal electrode pattern) that became an internal electrode after firing.
それから、内部電極パターンが形成されたセラミックグリーンシートを、内部電極パターンが交互に逆側に引き出されるような態様で所定枚数積層し、さらに、上下両面側に、導電ペーストパターンが形成されていないセラミックグリーンシートを外層として積層することにより、積層ブロックを作製した。 Then, a predetermined number of ceramic green sheets on which internal electrode patterns are formed are stacked in such a manner that the internal electrode patterns are alternately drawn to the opposite side, and further, a ceramic in which no conductive paste pattern is formed on both upper and lower sides A laminated block was produced by laminating green sheets as outer layers.
なお、この実施例では、内部電極パターンが形成されたセラミックグリーンシートを、有効誘電体層（コンデンサ形成層）の層数が１００層となるように積層した。 In this example, the ceramic green sheets on which the internal electrode patterns were formed were laminated so that the number of effective dielectric layers (capacitor forming layers) was 100.
次ぎに、この積層ブロックを所定の寸法となるようにカットすることにより得た未焼成の積層体を、大気中で３００℃に加熱してバインダーを燃焼させた後、酸素分圧１０-10ＭＰａのＨ2−Ｎ2−Ｈ2Ｏガスからなる還元性雰囲気中で、１２００℃、２時間の条件で焼成し、焼成済みの積層体（セラミック積層体）を得た。 Next, an unfired laminated body obtained by cutting the laminated block to a predetermined size is heated to 300 ° C. in the air to burn the binder, and then the oxygen partial pressure is 10 −10 MPa. Was fired at 1200 ° C. for 2 hours in a reducing atmosphere composed of H 2 —N 2 —H 2 O gas to obtain a fired laminate (ceramic laminate).
それから、焼成済みのセラミック積層体の、内部電極が引き出された両端面に、導電成分である銅粉末と、Ｂ2Ｏ3−Ｌｉ2Ｏ−ＳｉＯ2−ＢａＯ系のガラスフリットとを含有する導電ペーストを塗布した後、８００℃で焼き付けることにより、内部電極と電気的に接続された外部電極を形成した。 Then, conductive materials containing copper powder as a conductive component and glass frit of B 2 O 3 —Li 2 O—SiO 2 —BaO are formed on both end faces of the fired ceramic laminate from which internal electrodes are drawn. After applying the paste, an external electrode electrically connected to the internal electrode was formed by baking at 800 ° C.
これにより、図１に模式的に示すように、積層セラミック素子（焼成済みのセラミック積層体）１０の内部に配設された内部電極１２が、誘電体層（誘電体セラミック層）１１を介して積層され、かつ、積層セラミック素子１０の両端面には、交互に逆側の端面に露出した内部電極１２と導通するように一対の外部電極１３ａ，１３ｂが配設された構造を有する積層セラミックコンデンサを得た。 Thereby, as schematically shown in FIG. 1, the internal electrode 12 disposed inside the multilayer ceramic element (fired ceramic multilayer body) 10 passes through the dielectric layer (dielectric ceramic layer) 11. A laminated ceramic capacitor having a structure in which a pair of external electrodes 13a and 13b are arranged on both end faces of the laminated ceramic element 10 so as to be electrically connected to the internal electrodes 12 exposed on the opposite end faces alternately. Got.
なお、得られた積層セラミックコンデンサの外形寸法は、長さ：１．６ｍｍ、幅：０．８ｍｍ、厚さ：０．８ｍｍであり、内部電極１２間に介在する誘電体層（誘電体セラミック層）１１の厚みは１．０μｍであった。 The outer dimensions of the obtained multilayer ceramic capacitor are length: 1.6 mm, width: 0.8 mm, thickness: 0.8 mm, and a dielectric layer (dielectric ceramic layer) interposed between the internal electrodes 12. ) 11 had a thickness of 1.0 μm.
(Ｃ)特性の測定、誘電体セラミック層の構造分析、および評価
(１)特性の測定
上述のようにして作製した試料番号１〜２０の各試料（積層セラミックコンデンサ）について、室温での比誘電率、温度変化に対する静電容量の変化率（容量変化率）、寿命特性（高温負荷寿命）、およびバイアス特性を調べた。
(C) Measurement of characteristics, structural analysis of dielectric ceramic layer, and evaluation
(1) Measurement of characteristics For each of the samples Nos. 1 to 20 (multilayer ceramic capacitors) manufactured as described above, the relative permittivity at room temperature, the rate of change in capacitance with respect to temperature change (capacitance change rate), Life characteristics (high temperature load life) and bias characteristics were examined.
比誘電率は、温度２５℃，１ｋＨｚ，０．５Ｖｒｍｓの条件下で静電容量を測定し、得られた静電容量の値から計算した。各試料について調べた比誘電率の値を表２に示す。 The dielectric constant was calculated from the capacitance value obtained by measuring the capacitance under conditions of a temperature of 25 ° C., 1 kHz, and 0.5 Vrms. Table 2 shows the value of the relative dielectric constant examined for each sample.
また、温度変化に対する静電容量の変化率（容量変化率）は、２５℃での静電容量を基準とした−５５℃から１２５℃の温度範囲における変化率の最大値を示した。各試料について測定した静電容量の変化率を表２に併せて示す。
なお、−５５℃から１２５℃の範囲での変化率が±１５％以内であれば、ＥＩＡ規格のＸ７Ｒ特性を満足することになる。
Moreover, the change rate of capacitance with respect to temperature change (capacitance change rate) showed the maximum value of the change rate in the temperature range of −55 ° C. to 125 ° C. based on the capacitance at 25 ° C. Table 2 also shows the rate of change in capacitance measured for each sample.
If the rate of change in the range of −55 ° C. to 125 ° C. is within ± 15%, the X7R characteristic of the EIA standard is satisfied.
また，寿命特性（高温負荷寿命）は、それぞれ１００個の試料について、温度１５０℃で２０Ｖの電圧（２０ｋＶ／ｍｍ）を印加する高温負荷寿命試験を行い、２０００時間経過時点および３０００時間経過時点における絶縁抵抗値を調べ、絶縁抵抗値が２００ｋΩ以下になった試料を不良と判定した。なお、表２には、試験に供した１００個の試料のうち不良の発生した試料の個数の割合を示している。 Moreover, the life characteristics (high temperature load life) were obtained by conducting a high temperature load life test in which a voltage of 20 V (20 kV / mm) was applied at a temperature of 150 ° C. with respect to 100 samples, respectively, after 2000 hours and 3000 hours. The insulation resistance value was examined, and a sample having an insulation resistance value of 200 kΩ or less was determined to be defective. Table 2 shows the ratio of the number of defective samples among the 100 samples used for the test.
また、バイアス特性は、上述のようにして作製した試料番号１〜２０の各試料（積層セラミックコンデンサ）について、ＤＣバイアスを印加しない場合における静電容量と、ＤＣバイアス（ＤＣ４Ｖ）を印加した場合における静電容量を測定し、ＤＣバイアスの印加により静電容量が低下した割合を調べた。そして、静電容量が低下した割合をバイアス特性として表２に示した。 The bias characteristics of the samples Nos. 1 to 20 (multilayer ceramic capacitors) manufactured as described above are those obtained when a DC bias is not applied and when a DC bias (DC 4 V) is applied. The capacitance was measured, and the rate at which the capacitance decreased due to the application of a DC bias was examined. Table 2 shows the ratio of decrease in capacitance as bias characteristics.
(２)誘電体セラミック層の構造分析
上述のようにして作製した試料番号１〜２０の各試料（積層セラミックコンデンサ）を構成する誘電体セラミック層について、エネルギー分散型Ｘ線分光法（ＴＥＭ−ＥＤＸ）により、２ｎｍのプローブを用いてＲ成分およびＭ成分を定量し、それぞれの濃度分布を観察した。
(2) Structural analysis of dielectric ceramic layer For the dielectric ceramic layers constituting each sample (multilayer ceramic capacitor) of sample numbers 1 to 20 produced as described above, energy dispersive X-ray spectroscopy (TEM-EDX) ), The R component and the M component were quantified using a 2 nm probe, and the respective concentration distributions were observed.
なお、Ｒ成分およびＭ成分の定量（濃度の測定）は、図２に示すようにセラミック粒子の粒界から粒子中心までを１０等分し、各区分領域の両端側のポイントで行った。したがって、測定ポイントは１１ポイントとなる。 The R component and M component were quantitatively determined (concentration measurement) by dividing the ceramic particle from the grain boundary to the particle center into 10 equal parts as shown in FIG. Therefore, the measurement points are 11 points.
図３に、試料番号１の試料について上述の方法で測定した、濃度分布（各測定ポイントにおけるＲ成分とＭ成分の合計濃度の関係）を示す。 FIG. 3 shows the concentration distribution (relationship between the total concentration of the R component and M component at each measurement point) measured for the sample of sample number 1 by the method described above.
(３)評価
表２に示すように、試料番号１〜１９の試料はいずれも本発明の実施例にかかる試料であり、比誘電率が３５００以上と高く、容量温度特性がＸ７Ｒ特性を満足するものであることが確認された。
なお、表１の試料番号２０の比較例の試料も比誘電率および容量温度特性については、特に問題となるようなものではないことが確認された。
(3) Evaluation As shown in Table 2, all of the samples Nos. 1 to 19 are samples according to the examples of the present invention, the dielectric constant is as high as 3500 or more, and the capacity-temperature characteristic satisfies the X7R characteristic. It was confirmed to be a thing.
It was confirmed that the sample of Comparative Example No. 20 in Table 1 was not particularly problematic with respect to the relative dielectric constant and the capacity-temperature characteristic.
また、試料番号１〜１９の試料はいずれも、高温負荷寿命試験の２０００時間経過時点および３０００時間経過時点において絶縁抵抗値が２００ｋΩ以下になったものはなく（不良数がいずれも０個）、寿命特性は高水準であることが確認された。 In addition, none of the samples Nos. 1 to 19 had an insulation resistance value of 200 kΩ or less after 2000 hours and 3000 hours of the high temperature load life test (the number of defects was 0). It was confirmed that the life characteristics are at a high level.
また、試料番号１〜１９の試料はいずれも、エネルギー分散型Ｘ線分光法（ＴＥＭ−ＥＤＸ）によるＲ成分およびＭ成分の定量結果より、図３，図４，表３に示すように、誘電体セラミック層に、Ｒ成分とＭ成分の合計濃度の極小（極小値Ｃ２）となる部分と、極大（極大値Ｃ３）となる部分が存在することが確認された。なお、表３におけるＣ１，Ｃ２およびＣ３のｍｏｌ部は、主成分（ＢａＴｉＯ3系粉末）１００ｍｏｌ部に対する割合である。 Moreover, as for the sample of sample numbers 1-19, as shown in FIG. 3, FIG. 4, Table 3 from the fixed_quantity | quantitative_assay result of R component and M component by energy dispersive X-ray spectroscopy (TEM-EDX), as shown in FIG. It was confirmed that the body ceramic layer has a portion where the total concentration of the R component and the M component is minimized (minimum value C2) and a portion where the concentration is maximum (maximum value C3). In Table 3, the mol parts of C1, C2, and C3 are ratios relative to 100 mol parts of the main component (BaTiO 3 -based powder).
なお、図４は、本発明の実施例にかかる誘電体セラミック粒子（試料番号１の試料）の構成と、シェル部におけるＲ成分とＭ成分の合計濃度の分布状態を示す図である。そして、図４に示すように、誘電体セラミック粒子２０は、シェル部２２においてＲ成分とＭ成分が検出され、粒界２５からコア部２１に向かって、Ｒ成分とＭ成分の合計濃度に勾配があり、かつ、シェル部２２に、Ｒ成分とＭ成分の合計濃度の極小値Ｃ２と極大値Ｃ３が存在するとともに、極大値Ｃ３が、粒界２５におけるＲ成分とＭ成分の合計濃度の値Ｃ１より小さいという、本発明の特徴的な構成を備えている。 FIG. 4 is a diagram showing the configuration of the dielectric ceramic particles (sample No. 1) according to the example of the present invention and the distribution state of the total concentration of the R component and the M component in the shell portion. As shown in FIG. 4, the dielectric ceramic particle 20 has an R component and an M component detected in the shell portion 22, and a gradient of the total concentration of the R component and the M component from the grain boundary 25 toward the core portion 21. In addition, the shell portion 22 has the minimum value C2 and the maximum value C3 of the total concentration of the R component and the M component, and the maximum value C3 is the value of the total concentration of the R component and the M component at the grain boundary 25. It has a characteristic configuration of the present invention that is smaller than C1.
一方、試料番号２０の試料の誘電体層（誘電体セラミック層）は、ＢａＴｉＯ3粉末に、Ｒ成分の酸化物粉末、Ｍ成分の酸化物粉末およびＳｉＯ2粉末を配合し、混合、乾燥することにより製造された誘電体配合原料粉末を用いてなるセラミックグリーンシートを積層、焼成することにより形成されたものであって、コアシェル構造粒子からなる誘電体材料であるが、表３に示すように、Ｒ成分とＭ成分の合計濃度の極小となる部分および極大となる部分を備えていない材料であることから、高温負荷寿命試験において、２０００時間以上の信頼性（寿命）レベルは満足できたが、３０００時間経過時点では、１００個の試料中１４個の試料に不良が発生し、寿命特性には改善の余地があることが確認された。 On the other hand, the dielectric layer (dielectric ceramic layer) of the sample of sample number 20 is a mixture of BaTiO 3 powder, R component oxide powder, M component oxide powder and SiO 2 powder, mixed and dried. It is formed by laminating and firing a ceramic green sheet using a dielectric compound raw material powder produced by the above, and is a dielectric material composed of core-shell structured particles, but as shown in Table 3, Since it is a material that does not have the minimum and maximum portions of the total concentration of the R component and the M component, the reliability (life) level of 2000 hours or more was satisfied in the high temperature load life test, When 3000 hours passed, defects occurred in 14 samples out of 100 samples, and it was confirmed that there was room for improvement in life characteristics.
また、試料番号１〜８，１０，１２〜１９については、Ｒ成分とＭ成分の合計濃度が極大となる部分の値である極大値Ｃ３が、粒界におけるＲ成分とＭ成分の合計濃度の値Ｃ１よりも小さくなっており、良好なバイアス特性が得られる（ＤＣ４Ｖを印加したときの静電容量の変化率が小さい）ことが確認された。 For sample numbers 1 to 8, 10, 12 to 19, the maximum value C3, which is the value of the portion where the total concentration of the R component and the M component is maximum, is the total concentration of the R component and the M component at the grain boundary. It was smaller than the value C1, and it was confirmed that good bias characteristics can be obtained (the rate of change in capacitance when DC4V is applied is small).
また、この実施例の試料番号1〜１９の試料では、表３に示すようにＲ成分とＭ成分の合計濃度が極小となる部分の値である極小値Ｃ２と、極大となる部分の値である極大値Ｃ３の比率Ｃ２／Ｃ３の値が０．２４〜０．７４の範囲にあるが、極小値Ｃ２と、極大値Ｃ３の比率Ｃ２／Ｃ３は、通常、０．６０以下の範囲にあることが望ましい。 Further, in the samples of sample numbers 1 to 19 of this example, as shown in Table 3, a minimum value C2 which is a value where the total concentration of the R component and the M component becomes a minimum, and a value where the maximum value is obtained. The ratio C2 / C3 of a certain maximum value C3 is in the range of 0.24 to 0.74, but the ratio C2 / C3 of the minimum value C2 and the maximum value C3 is usually in the range of 0.60 or less. It is desirable.
また、この実施例では、シェル部に、Ｒ成分とＭ成分の合計濃度が極小となる部分および極大となる部分がそれぞれ１つずつである場合を例にとって説明したが、極小となる部分と極大となる部分の少なくとも一方を２つ以上存在するようにしてもよい。 Further, in this embodiment, the case where the shell portion has one portion where the total concentration of the R component and the M component is minimized and one portion where the concentration is maximized is described as an example. There may be two or more of at least one of the parts.
また、本発明においては、ＢａＴｉＯ3系セラミック粒子を構成するＢａの一部をＣａおよび／またはＳｒで置換したり、Ｔｉの一部をＺｒおよび／またはＨｆで置換したりすることも可能であり、その場合には、特性を制御して、所望の特性を備えた誘電体セラミックを得ることができる。 In the present invention, part of Ba constituting the BaTiO 3 ceramic particles can be replaced with Ca and / or Sr, or part of Ti can be replaced with Zr and / or Hf. In that case, it is possible to obtain a dielectric ceramic having desired characteristics by controlling the characteristics.
また、この実施例では、本発明の誘電体セラミックを、積層セラミックコンデンサの誘電体層として用いる場合を例にとって説明したが、本発明にかかる誘電体セラミックは、積層セラミックコンデンサに限らず、ＬＣ複合部品などにも適用することが可能である。 Further, in this embodiment, the case where the dielectric ceramic of the present invention is used as a dielectric layer of a multilayer ceramic capacitor has been described as an example. However, the dielectric ceramic according to the present invention is not limited to a multilayer ceramic capacitor, and is an LC composite. It can also be applied to parts.
本発明はさらにその他の点においても上記実施例に限定されるものではなく、本発明の誘電体セラミックを製造する場合の各原料の種類、製造工程の具体的な条件、Ｒ成分、Ｍ成分などの具体的な配合割合などに関し、発明の範囲内において種々の応用、変形を加えることが可能である。 The present invention is not limited to the above-described embodiments in other points. Kinds of raw materials, specific conditions of the manufacturing process, R component, M component, etc. when the dielectric ceramic of the present invention is manufactured. Various applications and modifications can be made within the scope of the invention with respect to the specific blending ratio of the above.
１０ 積層セラミック素子
１１ セラミック層
１２ 内部電極層
１３ａ，１３ｂ 外部電極
２０ セラミック粒子
２１ コア部
２２ シェル部
２５ 粒界
Ｃ１ 粒界におけるＲ成分とＭ成分の合計濃度
Ｃ２ Ｒ成分とＭ成分の合計濃度の極小となる部分（極小値）
Ｃ３ Ｒ成分とＭ成分の合計濃度の極大となる部分（極大値）
DESCRIPTION OF SYMBOLS 10 Multilayer ceramic element 11 Ceramic layer 12 Internal electrode layer 13a, 13b External electrode 20 Ceramic particle 21 Core part 22 Shell part 25 Grain boundary C1 Total density | concentration of R component and M component in a grain boundary C2 Sum total density | concentration of R component and M component Minimal part (minimum value)
C3 Maximum portion of the total concentration of R and M components (maximum value)
Claims (5)
前記ＢａＴｉＯ3系セラミック粒子は、表層部であるシェル部と、シェル部の内側のコア部とを備え、
副成分として、Ｒ（Ｒは、希土類元素であって、Ｎｄ，Ｓｍ，Ｅｕ，Ｇｄ，Ｔｂ，Ｄｙ，Ｈｏ，ＥｒおよびＹからなる群より選ばれる少なくとも１種）、および、Ｍ（Ｍは、Ｍｇ，Ｍｎ，Ｎｉ，Ｃｏ，Ｆｅ，Ｃｒ，Ｃｕ，Ａｌ，Ｍｏ，ＷおよびＶからなる群より選ばれる少なくとも１種）を含み、
前記ＢａＴｉＯ3系セラミック粒子の前記シェル部が、前記Ｒおよび前記Ｍを含むとともに、前記Ｒおよび前記Ｍの合計濃度は、粒界から前記コア部に向かって勾配を有し、かつ、極小となる部分と、極大となる部分とを有していること
を特徴とする誘電体セラミック。 It consists of a sintered body with BaTiO 3 ceramic particles as main phase particles,
The BaTiO 3 based ceramic particles include a shell portion that is a surface layer portion and a core portion inside the shell portion,
As subcomponents, R (R is a rare earth element and is at least one selected from the group consisting of Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, and Y), and M (M is Mg, Mn, Ni, Co, Fe, Cr, Cu, Al, Mo, W, and V).
The shell portion of the BaTiO 3 based ceramic particles includes the R and the M, and the total concentration of the R and the M has a gradient from the grain boundary toward the core portion, and is minimal. A dielectric ceramic characterized by having a portion and a maximum portion.
を特徴とする請求項１記載の誘電体セラミック。 In the BaTiO 3 ceramic particles, a part of Ba is substituted with Ca and / or Sr, and / or a part of Ti is substituted with Zr and / or Hf. Item 2. The dielectric ceramic according to Item 1.
前記誘電体層が、請求項１〜４のいずれかに記載の誘電体セラミックから形成されていること
を特徴とする積層セラミックコンデンサ。 A multilayer ceramic capacitor having a structure in which a plurality of dielectric layers and a plurality of internal electrodes are integrally laminated,
A multilayer ceramic capacitor, wherein the dielectric layer is formed of the dielectric ceramic according to any one of claims 1 to 4.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| KR20160079630A (en) | 2014-12-26 | 2016-07-06 | 다이요 유덴 가부시키가이샤 | Multilayer ceramic capacitor |
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