JP2005187218A - Dielectric porcelain, laminated electronic component, and production method for laminated electronic component - Google Patents
Dielectric porcelain, laminated electronic component, and production method for laminated electronic component Download PDFInfo
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本発明は、誘電体磁器および積層型電子部品並びにその製法に関し、特に、より詳細には、例えば、誘電体層に印加される直流電圧が２Ｖ／μｍ以上であるような高電圧用の積層セラミックコンデンサ等の形成に特に有用な誘電体磁器、および該誘電体磁器を用いて形成された積層型電子部品、並びにその製法に関する。 The present invention relates to a dielectric ceramic, a multilayer electronic component, and a method for manufacturing the same, and more particularly, for example, a high voltage multilayer ceramic in which a DC voltage applied to a dielectric layer is 2 V / μm or more. The present invention relates to a dielectric ceramic particularly useful for forming capacitors and the like, a multilayer electronic component formed using the dielectric ceramic, and a method for manufacturing the same.
積層セラミックコンデンサ（ＭＬＣ）の誘電体層の形成に使用される誘電体材料には、小型、高容量化の為に、高い比誘電率が要求されるのはもちろんのこと、誘電損失が小さく、誘電特性の温度に対する依存性（温度依存性）や直流電圧に対する依存性（ＤＣバイアス依存性）が小さい等の種々の特性が要求される。 A dielectric material used for forming a dielectric layer of a multilayer ceramic capacitor (MLC) is required to have a high relative dielectric constant for miniaturization and high capacity, as well as low dielectric loss. Various characteristics are required such that the dependence of dielectric characteristics on temperature (temperature dependence) and dependence on DC voltage (dependence on DC bias) are small.
また、誘電体層の薄層化に伴い、積層セラミックコンデンサに印加する電界の増大による信頼性低下を抑制するために、粒子径のより小さい誘電体材料が使用されるようになってきているが、例えば、下記の特許文献１によれば、水熱合成法や加水分解法などの製法により調製した原料粉末を用いることにより、焼結後においてもサブミクロン粒径の主結晶粒子を有する誘電体層が得られている。 In addition, with the thinning of the dielectric layer, a dielectric material having a smaller particle diameter has been used in order to suppress a decrease in reliability due to an increase in the electric field applied to the multilayer ceramic capacitor. For example, according to the following Patent Document 1, by using a raw material powder prepared by a manufacturing method such as a hydrothermal synthesis method or a hydrolysis method, a dielectric having main crystal particles having a submicron particle size even after sintering A layer is obtained.
一方、上述のような誘電体層を有する積層セラミックコンデンサにおいて、誘電体層の薄層化に伴うデラミネーションの発生を防止するために、誘電体層を構成するＢａＴｉＯ３を主成分とする誘電体磁器中にＡｌ２Ｏ３などの副成分を添加することが記載されている（例えば、特許文献２）。
しかしながら、上記特許文献１に開示された誘電体磁器は、厚みが３μｍと薄層化され、主結晶粒子の平均粒径が０．１〜０．３μｍであり、また、温度特性の異なる２種類以上の微細な主結晶粒子により構成され、温度依存性が小さくなっているものの、このような粒子サイズでは、最大でも２１００程度の比誘電率しか得られず、高容量化に限界があった。 However, the dielectric ceramic disclosed in Patent Document 1 has a thickness as thin as 3 μm, an average grain size of main crystal grains of 0.1 to 0.3 μm, and two types having different temperature characteristics. Although it is composed of the above fine main crystal particles and the temperature dependence is small, with such a particle size, only a relative dielectric constant of about 2100 is obtained at the maximum, and there is a limit to increasing the capacity.
また、この特許文献１にて用いられる原料のように、粒子サイズが０．３μｍ以下になると、焼結時に容易に固溶体を形成し粒成長してしまうため、原料粒子サイズを維持したまま緻密な焼結体を作製することが極めて困難であり、このような誘電体磁器を用いて作製された積層セラミックコンデンサは、焼成時や外部電極形成時にチッピング（欠け）しやすいという問題が生じていた。 In addition, as in the raw material used in Patent Document 1, when the particle size is 0.3 μm or less, a solid solution is easily formed during grain growth and grain growth occurs. It is extremely difficult to produce a sintered body, and a multilayer ceramic capacitor produced using such a dielectric ceramic has a problem that it tends to chip (chip) during firing or external electrode formation.
一方、特許文献２にかかるＡｌ２Ｏ３を添加した誘電体磁器は、高い比誘電率を有するものであるが、そもそも、このような磁器は、特許文献２に記載の製法によれば、Ａｌ２Ｏ３を、ＢａＣＯ３、ＴｉＯ２、ＭｎＣＯ３およびＭｇＯなどの各種素原料とともに一括で混合し、仮焼、焼成されたものであり、このような製法により形成された誘電体磁器では、主成分であるＢａＴｉＯ３の主結晶粒子の内部にＡｌ２Ｏ３が固溶しており、高い比誘電率は得られるものの、反面、比誘電率の温度依存性が大きいという問題があった。 On the other hand, the dielectric porcelain to which Al 2 O 3 added according to Patent Document 2 has a high relative dielectric constant. However, according to the manufacturing method described in Patent Document 2, such a porcelain is basically made of Al 2 O 3. 2 O 3 is mixed together with various raw materials such as BaCO 3 , TiO 2 , MnCO 3, and MgO at one time, calcined, and baked. In a dielectric ceramic formed by such a manufacturing method, Although Al 2 O 3 is dissolved in the main crystal grains of the component BaTiO 3 and a high relative dielectric constant is obtained, there is a problem that the temperature dependence of the relative dielectric constant is large.
従って、本発明は、結晶粒子を微細化しても高い比誘電率を維持し、比誘電率の温度依存性が小さく、また、チッピングのない誘電体磁器および積層型電子部品ならびに積層型電子部品の製法を提供することを目的とする。 Therefore, the present invention maintains a high relative dielectric constant even when crystal grains are miniaturized, the temperature dependence of the relative dielectric constant is small, and there are no chipping dielectric ceramics and multilayer electronic components and multilayer electronic components. The purpose is to provide a manufacturing method.
本発明の誘電体磁器は、金属元素として、少なくともＢａ、Ｔｉ、希土類元素、ＭｇおよびＭｎを含有するペロブスカイト型複合酸化物からなる主結晶粒子と、粒界相とからなる誘電体磁器において、前記主結晶粒子及び粒界相中にＡｌを含み、酸化物換算したときのＡｌの含有量が、前記主結晶粒子の内部が０．０１質量％以下、粒界相が０．０５〜２質量％であることを特徴とする。 The dielectric ceramic of the present invention is a dielectric ceramic comprising a main crystal particle made of a perovskite complex oxide containing at least Ba, Ti, rare earth elements, Mg and Mn as a metal element, and a grain boundary phase. The main crystal particles and the grain boundary phase contain Al, and the content of Al when converted to oxide is 0.01% by mass or less for the inside of the main crystal particle and 0.05 to 2% by mass for the grain boundary phase. It is characterized by being.
このような構成によれば、誘電体磁器中に含まれるＡｌ成分を粒子内から極力排除し、一方、粒界に適正量を介在させることにより、主結晶粒子の比誘電率の低下を抑制しつつ、比誘電率の温度依存性を小さくし、かつ主結晶粒子の焼結性を高めチッピングなどの欠陥の発生を防止できる。 According to such a configuration, the Al component contained in the dielectric ceramic is eliminated as much as possible from the inside of the grain, and on the other hand, the appropriate amount is interposed at the grain boundary, thereby suppressing the decrease in the relative dielectric constant of the main crystal grain. However, it is possible to reduce the temperature dependence of the relative dielectric constant and to enhance the sinterability of the main crystal particles to prevent the occurrence of defects such as chipping.
上記誘電体磁器では、主結晶粒子は、その表面にＭ４Ｒ６Ｏ（ＳｉＯ４）型構造（Ｍはアルカリ土類元素、Ｒは希土類元素）の複合酸化物からなる被覆層を有することが望ましい。 In the dielectric ceramic, the main crystal particles may have a coating layer made of a complex oxide of M 4 R 6 O (SiO 4 ) type structure (M is an alkaline earth element and R is a rare earth element) on the surface thereof. desirable.
本発明の誘電体磁器において、特に、主結晶粒子表面に、アルカリ土類元素、希土類元素およびＳｉからなる複合酸化物を形成すると、この複合酸化物が比較的高い絶縁抵抗を有するため、誘電体層１層当たりの電界強度を高め、誘電体磁器の絶縁破壊電圧を高めることができ、誘電体層を薄層化しても静電容量の温度特性を向上できる。 In the dielectric ceramic according to the present invention, in particular, when a complex oxide composed of an alkaline earth element, a rare earth element and Si is formed on the surface of the main crystal particle, the complex oxide has a relatively high insulation resistance. The electric field strength per layer can be increased, the dielectric breakdown voltage of the dielectric ceramic can be increased, and the temperature characteristics of the capacitance can be improved even if the dielectric layer is thinned.
上記誘電体磁器では、主結晶粒子の平均粒径が０．１〜０．４μｍであり、ｃ軸／ａ軸比が１．００５以上であることが望ましい。このように微細結晶粒子においても高い正方晶性を有することで、高い誘電率を実現することができる。 In the dielectric ceramic, it is desirable that the average grain size of the main crystal grains is 0.1 to 0.4 μm and the c-axis / a-axis ratio is 1.005 or more. Thus, a high dielectric constant can be realized by having high tetragonal properties even in the fine crystal particles.
上記誘電体磁器では、主結晶粒子を構成するＢａ元素が３０原子％以下の比率でＣａ元素に置換されていることが望ましい。主結晶粒子の一部あるいは全部のＢａ元素が３０原子％以下の比率でＣａ元素に置き換えることにより、比誘電率の温度特性をさらに平坦化することができる。 In the dielectric ceramic, it is desirable that the Ba element constituting the main crystal particle is replaced with Ca element at a ratio of 30 atomic% or less. By replacing some or all of the Ba elements of the main crystal grains with Ca elements at a ratio of 30 atomic% or less, the temperature characteristics of the dielectric constant can be further flattened.
つまり、上記誘電体磁器では、比誘電率の温度特性が、ＪＩＳ規格のＢ特性（−２５〜８５℃において、±１５％以内）であることが望ましく、さらには、２５℃における比誘電率が２５００以上であることが望ましい。 That is, in the dielectric ceramic, it is desirable that the temperature characteristic of the relative dielectric constant is a JIS standard B characteristic (within ± 15% at −25 to 85 ° C.), and further, the relative dielectric constant at 25 ° C. It is desirable that it is 2500 or more.
本発明の積層型電子部品は、誘電体層と内部電極層とを交互に積層してなる電子部品本体を備えた積層型電子部品であって、前記誘電体層が上記の誘電体磁器からなることを特徴とするものであり、特に、誘電体層の厚みが３μｍ以下であることが望ましい。 The multilayer electronic component of the present invention is a multilayer electronic component having an electronic component body in which dielectric layers and internal electrode layers are alternately stacked, and the dielectric layer is made of the above dielectric ceramic. In particular, the thickness of the dielectric layer is desirably 3 μm or less.
本発明の誘電体磁器は、上記したように優れた特性を有するため、主結晶粒子を微細化して誘電体層を薄層化した積層型電子部品を形成したとしても、誘電特性や絶縁抵抗および誘電体磁器の絶縁破壊電圧を高め、誘電体層１層あたりの電界強度を向上することができ、誘電体層を薄層化しても静電容量の温度特性を向上でき、チッピングを抑制できる。 Since the dielectric ceramic of the present invention has excellent characteristics as described above, even if a multilayer electronic component in which the main crystal particles are refined and the dielectric layer is thinned is formed, the dielectric characteristics, insulation resistance and The dielectric breakdown voltage of the dielectric ceramic can be increased, the electric field strength per dielectric layer can be improved, and the temperature characteristics of the capacitance can be improved and chipping can be suppressed even if the dielectric layer is thinned.
本発明の積層型電子部品の製法は、ＢａＴｉＯ３からなる原料粉末の表面に、希土類元素、ＭｇおよびＭｎの混合物が被覆された被覆ＢａＴｉＯ３粉末と、アルカリ土類元素およびＳｉを含み、Ａｌを酸化物換算で０．０５〜２質量％含有する副成分とを混合し、この混合粉末に対して、少なくとも有機バインダおよび有機溶媒を加えて誘電体スラリーを調製する工程と、該誘電体スラリーを用いて誘電体グリーンシートを形成する工程と、該誘電体グリーンシートの主面上に内部電極パターンを形成する工程と、該内部電極パターンが形成された誘電体グリーンシートを複数積層して、積層成形体を作製する工程と、該積層成形体を焼成する工程とを具備することを特徴とする。 Preparation of multilayer electronic component of the present invention, the surface of the raw material powder composed of BaTiO 3, a rare earth element, and a covering BaTiO 3 powder mixture of Mg and Mn is coated includes an alkaline-earth element and Si, the Al A step of preparing a dielectric slurry by mixing at least an organic binder and an organic solvent with respect to the mixed powder, and a subcomponent containing 0.05 to 2% by mass in terms of oxide, A step of forming a dielectric green sheet, a step of forming an internal electrode pattern on a main surface of the dielectric green sheet, and a plurality of dielectric green sheets each having the internal electrode pattern formed thereon It comprises a step of producing a molded body and a step of firing the laminated molded body.
この製法において、先ず、ＢａＴｉＯ３からなる原料粉末の表面に、希土類元素、Ｍｇ、およびＭｎの混合物を被覆し、次に、この被覆ＢａＴｉＯ３粉末にＡｌ２Ｏ３などの添加物成分を添加することにより、ＢａＴｉＯ３からなる主結晶粒子の表面にほぼ均一に高絶縁性の複合酸化物からなる被覆層を形成できる。このため、主結晶粒子が小さくても後に添加するＡｌ２Ｏ３などの添加物の主結晶粒子への固溶を抑制でき、一方で、添加したＡｌ２Ｏ３を粒界相に偏析させることにより、誘電体層の比誘電率を高く維持したまま、薄層化した誘電体層の１層あたりの電界強度を高め、また絶縁破壊電圧を高め、さらには積層型電子部品の静電容量の温度特性を改善でき、チッピングの発生をも抑制することができる。 In this production method, first, a mixture of rare earth elements, Mg, and Mn is coated on the surface of a raw material powder made of BaTiO 3 , and then an additive component such as Al 2 O 3 is added to the coated BaTiO 3 powder. As a result, a coating layer made of a complex oxide having high insulating properties can be formed almost uniformly on the surface of the main crystal particles made of BaTiO 3 . For this reason, even if the main crystal particles are small, solid solution of additives such as Al 2 O 3 added later to the main crystal particles can be suppressed, while the added Al 2 O 3 is segregated to the grain boundary phase. Thus, while maintaining the dielectric constant of the dielectric layer high, the electric field strength per layer of the thinned dielectric layer is increased, the dielectric breakdown voltage is increased, and the capacitance of the multilayer electronic component is further increased. The temperature characteristics can be improved and the occurrence of chipping can also be suppressed.
即ち、本発明によれば、ＢａＴｉＯ３からなる原料粉末の表面に、希土類元素、ＭｇおよびＭｎの混合物が被覆された被覆ＢａＴｉＯ３粉末と、アルカリ土類元素およびＳｉを含み、Ａｌを酸化物換算で０．０５〜２質量％含有する副成分とを混合したものを焼成し、結果として、酸化物換算したときのＡｌの含有量が、主結晶粒子の内部のＡｌ酸化物の含有量が０．０１質量％以下、粒界相が０．０５〜２質量％とすることにより、主結晶粒子の比誘電率の低下を抑制しつつ、比誘電率の温度依存性を小さくし、絶縁抵抗や絶縁破壊電圧を高め、かつ主結晶粒子の焼結性を高めチッピングなどの欠陥の発生を防止できる。 That is, according to the present invention, the surface of the raw material powder composed of BaTiO 3, wherein the rare earth element, and a covering BaTiO 3 powder mixture is coated of Mg and Mn, the alkaline earth elements and Si, in terms of oxide of Al As a result, the content of Al when converted to oxide is 0, and the content of Al oxide inside the main crystal particles is 0. .01% by mass or less and the grain boundary phase is 0.05 to 2% by mass, while suppressing the decrease in the dielectric constant of the main crystal grains, the temperature dependence of the dielectric constant is reduced, and the insulation resistance and It is possible to increase the dielectric breakdown voltage, increase the sinterability of the main crystal particles, and prevent the occurrence of defects such as chipping.
本発明の誘電体磁器は金属元素として、少なくともＢａ、Ｔｉ、希土類元素、ＭｇおよびＭｎを含有するペロブスカイト型複合酸化物からなる主結晶粒子と、粒界相とからなる誘電体磁器であって、主結晶粒子内部にＡｌ元素を酸化物換算で０．０１質量％以下であるとともに、粒界相に平均してＡｌ元素を酸化物換算で０．０５質量％から２．０質量％の割合で含有することにより優れた特性を示す。 The dielectric porcelain of the present invention is a dielectric porcelain comprising main crystal particles made of a perovskite complex oxide containing at least Ba, Ti, rare earth elements, Mg and Mn as metal elements, and a grain boundary phase, In the main crystal grains, the Al element is 0.01% by mass or less in terms of oxide, and the Al element is averaged in the grain boundary phase at a ratio of 0.05% to 2.0% by mass in terms of oxide. By containing, it exhibits excellent characteristics.
主結晶粒子は、ＢａＴｉＯ３系のペロブスカイト型複合酸化物またはＢａの一部がＣａで置換されたペロブスカイト型複合酸化物さらにはその混合物であってもよい。主結晶粒子のＢサイトには、通常、Ｍｇ、Ｍｎ及び希土類元素が固溶している。また、この主結晶粒子表面にはアルカリ土類元素、希土類元素およびＳｉを含有する複合酸化物からなる被覆層が形成されており、該被覆層がＭ４Ｒ６Ｏ（ＳｉＯ４）型構造（Ｍはアルカリ土類元素、Ｒは希土類元素）を有する。この被覆層は主結晶粒子の全周を取り囲むように形成されている。この被覆層を含め、主結晶粒子内部に含有するＡｌ元素は、酸化物に換算して０．０１質量％以下であることが重要である。それ以上Ａｌが主結晶相に含有された場合、特に、微小粒子の場合には比誘電率の低下が著しく、積層型電子部品としての使用に耐えない。特に、主結晶相に含有されるＡｌ量は０．００５質量％以下であることが好ましい。 The main crystal particles may be a BaTiO 3 -based perovskite complex oxide, a perovskite complex oxide in which a part of Ba is substituted with Ca, or a mixture thereof. Usually, Mg, Mn, and rare earth elements are dissolved in the B site of the main crystal particle. Further, a coating layer made of a complex oxide containing an alkaline earth element, a rare earth element and Si is formed on the surface of the main crystal particle, and the coating layer has an M 4 R 6 O (SiO 4 ) type structure ( M is an alkaline earth element, and R is a rare earth element. This coating layer is formed so as to surround the entire circumference of the main crystal particle. It is important that the Al element contained in the main crystal grains including this coating layer is 0.01% by mass or less in terms of oxide. When Al is further contained in the main crystal phase, particularly in the case of fine particles, the relative permittivity is remarkably lowered, and cannot be used as a multilayer electronic component. In particular, the amount of Al contained in the main crystal phase is preferably 0.005% by mass or less.
一方、粒界相は、例えば、Ｃａ４Ｙ６Ｏ（ＳｉＯ４）結晶相や、他のＣａ、Ｙ、Ｓｉ、およびＬｉ等を含む化合物から構成されており、この化合物に、平均して０．０５質量％から２．０質量％の割合でＡｌ元素が酸化物換算で含有されることにより、粒界相の強度、靱性が向上しチッピングの発生が抑制される。特に、粒界相の絶縁性、強度、靱性を考慮すると、Ａｌ含有量は０．０７〜１．５質量％であることが望ましい。 On the other hand, the grain boundary phase is composed of, for example, a Ca 4 Y 6 O (SiO 4 ) crystal phase or a compound containing other Ca, Y, Si, Li, and the like. When the Al element is contained in an oxide conversion at a ratio of 0.05 mass% to 2.0 mass%, the strength and toughness of the grain boundary phase is improved and the occurrence of chipping is suppressed. In particular, when considering the insulation, strength, and toughness of the grain boundary phase, the Al content is preferably 0.07 to 1.5 mass%.
これに対して、主結晶粒子内部のＡｌ２Ｏ３含有量が０．０１質量％より多い場合には、比誘電率の温度依存性が大きくなる。 On the other hand, when the content of Al 2 O 3 in the main crystal particles is more than 0.01% by mass, the temperature dependence of the dielectric constant is increased.
粒界相におけるＡｌ２Ｏ３含有量が０．０５質量％より少ない場合には、誘電体磁器の強度が低下しチッピングしやすくなる。また、この粒界相におけるＡｌ２Ｏ３含有量が２質量％より多い場合には、誘電体磁器の比誘電率が低下する。 When the content of Al 2 O 3 in the grain boundary phase is less than 0.05% by mass, the strength of the dielectric ceramic decreases and chipping is likely to occur. Further, when the Al 2 O 3 content in the grain boundary phase is more than 2% by mass, the dielectric constant of the dielectric ceramic is lowered.
Ｍｇ、Ｍｎについては、殆どが主結晶粒子内に固溶するが、一部粒界に存在し、非晶質相を形成する場合がある。また、結晶相や被覆層を構成するこのＣａ４Ｙ６Ｏ（ＳｉＯ４）結晶相中のＹの代わりに、他の希土類元素を用いても同様の複合酸化物を形成することができるが、Ｃａ４Ｙ６Ｏ（ＳｉＯ４）結晶相と同じ結晶構造を持つ複合酸化物を形成する点から、Ｙ、Ｄｙ、およびＨｏが望ましく、特に、高誘電率化という点からＹが望ましい。 Most of Mg and Mn are dissolved in the main crystal grains, but some of them are present at the grain boundaries and an amorphous phase may be formed. Further, in place of Y in the Ca 4 Y 6 O (SiO 4 ) crystal phase constituting the crystal phase and the coating layer, a similar complex oxide can be formed by using other rare earth elements, Y, Dy, and Ho are desirable from the viewpoint of forming a composite oxide having the same crystal structure as the Ca 4 Y 6 O (SiO 4 ) crystal phase, and Y is particularly desirable from the viewpoint of increasing the dielectric constant.
一方、このＣａ４Ｙ６Ｏ（ＳｉＯ４）結晶相中のＣａの代わりに、他のアルカリ土類元素を用いても同様の複合酸化物を形成することができるが、Ｃａ４Ｙ６Ｏ（ＳｉＯ４）結晶相と同じ結晶構造を持つ複合酸化物を形成する点から、ＣａもしくはＳｒが望ましく、特に、高い電界強度を有するために高絶縁抵抗化という点からＣａが望ましい。 On the other hand, similar complex oxides can be formed by using other alkaline earth elements in place of Ca in the Ca 4 Y 6 O (SiO 4 ) crystal phase, but Ca 4 Y 6 O ( Ca or Sr is desirable from the viewpoint of forming a composite oxide having the same crystal structure as the SiO 4 ) crystal phase, and in particular, Ca is desirable from the viewpoint of high insulation resistance because it has a high electric field strength.
これらの主結晶粒子から構成されるシート状の誘電体層１層の厚みは３μｍ以下とされている。積層型電子部品Ａ、例えば、積層セラミックコンデンサの大容量化に対して、誘電体層を薄層化することは効果的な手段であり、近年の小型、高容量の積層セラミックコンデンサを構成するためには、その誘電体層厚みは、静電容量の向上の点で薄層化することが、絶縁性向上の点で厚みの確保が必要であり、よって１〜３μｍが好適である。 The thickness of one sheet-like dielectric layer composed of these main crystal particles is 3 μm or less. To increase the capacity of a multilayer electronic component A, for example, a multilayer ceramic capacitor, it is an effective means to make the dielectric layer thin, and in order to construct a recent small size and high capacity multilayer ceramic capacitor. In order to improve the insulation, it is necessary to secure the thickness of the dielectric layer from the viewpoint of improving the electrostatic capacity. Therefore, the thickness is preferably 1 to 3 μm.
また、主結晶粒子の平均粒径は高い絶縁抵抗を有するという理由から１μｍ以下、誘電体層を３μｍ以下とするためには、特には０．１〜０．４μｍの範囲が望ましい。さらに、このような粒径で高い誘電率を発現するために、結晶粒子の正方晶性はｃ軸／ａ軸比が１．００５以上であることが望ましい。ｃ軸／ａ軸比がこれよりも小さいと、必要な容量を得るために誘電体層は１μｍ以下となるが、粒成長、添加物の固溶が必要以上に進行しやすく、所望の温度特性が得られない場合がある。このように、誘電体層の厚みが３μｍ以下の薄い誘電体層の場合には、厚い誘電体層に対する絶縁抵抗よりも高い絶縁抵抗が要求されるが、本発明の誘電体磁器では、上記したように高い誘電率、絶縁抵抗を有するため、特に望ましい。 In addition, the average grain size of the main crystal grains is preferably in the range of 0.1 to 0.4 μm in order to have a high insulation resistance, and in order to make the dielectric layer 3 μm or less. Furthermore, in order to develop a high dielectric constant with such a particle size, it is desirable that the tetragonal crystallinity of the crystal particles has a c-axis / a-axis ratio of 1.005 or more. If the c-axis / a-axis ratio is smaller than this, the dielectric layer will be 1 μm or less in order to obtain the required capacity, but grain growth and solid solution of the additive will easily proceed more than necessary, and the desired temperature characteristics May not be obtained. As described above, in the case of a thin dielectric layer having a thickness of 3 μm or less, a dielectric resistance higher than that of the thick dielectric layer is required. It is particularly desirable because of its high dielectric constant and insulation resistance.
そして。このような誘電体磁器は積層セラミックコンデンサに代表されるような積層型電子部品に好適である。 And then. Such a dielectric ceramic is suitable for a multilayer electronic component represented by a multilayer ceramic capacitor.
即ち、本発明の積層型電子部品は、誘電体層と内部電極層とを交互に積層してなる電子部品本体５を備えてなるものである。 That is, the multilayer electronic component of the present invention comprises an electronic component body 5 formed by alternately laminating dielectric layers and internal electrode layers.
本発明の積層型電子部品は、先ず、誘電体層となるグリーンシートを作製する。このグリーンシートは、例えば、ＢａＴｉＯ３原料粉末を用いて形成する。 In the multilayer electronic component of the present invention, first, a green sheet to be a dielectric layer is produced. This green sheet is formed using, for example, BaTiO 3 raw material powder.
主原料のＢａＴｉＯ３粉の合成法は、固相法、液相法（シュウ酸塩を経過する方法等）、水熱合成法等があるが、そのうち粒度分布が狭く、結晶性が高いという理由から水熱合成法が望ましい。ＢａＴｉＯ３粉の比表面積は１．７〜１２．５（ｍ２／ｇ）、平均粒径は０．１〜０．４μｍが好ましい。 There are solid-phase method, liquid-phase method (method of passing oxalate, etc.), hydrothermal synthesis method, etc., as the main raw material BaTiO 3 powder synthesis method. Among them, the reason is that the particle size distribution is narrow and the crystallinity is high Therefore, hydrothermal synthesis is desirable. The specific surface area of the BaTiO 3 powder is preferably 1.7 to 12.5 (m 2 / g), and the average particle size is preferably 0.1 to 0.4 μm.
そして、本発明の誘電体磁器を作製するには、ＢａＴｉＯ３原料粉末として、その表面を希土類元素、Ｍｇ、Ｍｎの混合物で被覆したもの（以下、被覆ＢａＴｉＯ３粉ということもある）を用いることが重要である。このようなＢａＴｉＯ３原料粉末の被覆手法としては、固相法、液相法、気相法などがあるが、手法は特に限定されるものではない。上記のＢａＴｉＯ３粉の表面に形成された被覆膜は、希土類元素、Ｍｇ、Ｍｎの３種類の元素が混合されて、これらの元素が酸化物の状態で混在した状態となっていてもよいし、層状に形成されていてもよい。さらに、この被覆原料粉末を７００℃から１０００℃で熱処理し、被覆成分、特にＭｇ、Ｍｎを原料粉末粒子の外周部に固溶させることで他の添加成分が粒子内部に進入しにくくなる。 In order to produce the dielectric ceramic according to the present invention, a BaTiO 3 raw material powder whose surface is coated with a mixture of rare earth elements, Mg and Mn (hereinafter sometimes referred to as coated BaTiO 3 powder) is used. is important. Such a BaTiO 3 raw material coating method includes a solid phase method, a liquid phase method, a gas phase method, and the like, but the method is not particularly limited. The coating film formed on the surface of the BaTiO 3 powder may be a state in which three kinds of elements of rare earth elements, Mg, and Mn are mixed and these elements are mixed in an oxide state. However, it may be formed in layers. Furthermore, this coating raw material powder is heat-treated at 700 ° C. to 1000 ° C., and the coating components, particularly Mg and Mn, are dissolved in the outer periphery of the raw material powder particles, so that other additive components are less likely to enter the particles.
また、希土類元素、Ｍｇ、Ｍｎによる被覆量は、ＢａＴｉＯ３粉が１００重量部に対して酸化イットリウム（Ｙ２Ｏ３）を０．５〜１．５モル部、酸化マグネシウム（ＭｇＯ）を０．１〜０．３モル部、酸化マンガン（ＭｎＯ）を０．１〜０．３モル部の割合が望ましい。 Moreover, the coverage with rare earth elements, Mg, and Mn is 0.5 to 1.5 parts by mole of yttrium oxide (Y 2 O 3 ) and 0.1% of magnesium oxide (MgO) with respect to 100 parts by weight of BaTiO 3 powder. A proportion of 1 to 0.3 mol parts and 0.1 to 0.3 mol parts of manganese oxide (MnO) is desirable.
グリーンシートの誘電体磁器組成は、この被覆ＢａＴｉＯ３粉と、少なくともＬｉ２Ｏ、ＳｉＯ２、ＣａＯ、及び０．０５〜２質量％のＡｌ２Ｏ３を含む添加物成分（Ｌｉ、ＳｉおよびＣａのモル比が、それぞれ、０．９〜１．２：４．８〜５．３：０．５〜２．３）を、ＢａＴｉＯ３粉１００質量部に対して０．５〜２質量部添加して構成されている。なお、上記ＢａＴｉＯ３粉の他、その一部あるいは全部が、Ｂａの一部がＣａに置換された粉体を使用することもできる。 The dielectric ceramic composition of the green sheet is obtained by adding this coated BaTiO 3 powder and additive components (Li, Si and Ca) containing at least Li 2 O, SiO 2 , CaO, and 0.05 to 2 % by mass of Al 2 O 3. 0.5 to 2 parts by mass of 0.9 to 1.2: 4.8 to 5.3: 0.5 to 2.3) with respect to 100 parts by mass of BaTiO 3 powder, respectively. Configured. In addition to the BaTiO 3 powder, part or all of the BaTiO 3 powder may be powder in which part of Ba is replaced with Ca.
次に、上記グリーンシートに内部電極ペーストを塗布して内部電極パターンを形成し、これを乾燥させ、この内部電極パターンが形成されたグリーンシートを複数枚積層し、熱圧着させる。その後、この積層物を格子状に切断して、電子部品本体の成形体を得る。この電子部品本体の成形体の両端面には、内部電極パターンの端部が交互に露出している。 Next, an internal electrode paste is applied to the green sheet to form an internal electrode pattern, which is dried, and a plurality of green sheets on which the internal electrode pattern is formed are stacked and thermocompression bonded. Thereafter, the laminate is cut into a lattice shape to obtain a molded body of the electronic component main body. End portions of the internal electrode pattern are alternately exposed on both end faces of the molded body of the electronic component main body.
次に、この電子部品本体の成形体を大気中で５〜４０℃／ｈの昇温速度で２００〜４００℃にて脱バインダ処理を行い、その後、還元雰囲気中で少なくとも５００℃からの昇温速度を１００〜４００℃／ｈとし、１１００〜１３００℃の温度で２〜５時間焼成し、続いて１００〜４００℃／ｈの降温速度で冷却し、窒素雰囲気中９００〜１１００℃で再酸化処理を行う。 Next, the molded body of the electronic component main body is subjected to a binder removal treatment at 200 to 400 ° C. at a temperature rising rate of 5 to 40 ° C./h in the air, and then heated from at least 500 ° C. in a reducing atmosphere. The rate is set to 100 to 400 ° C./h, firing at a temperature of 1100 to 1300 ° C. for 2 to 5 hours, followed by cooling at a temperature lowering rate of 100 to 400 ° C./h, and reoxidation treatment at 900 to 1100 ° C. in a nitrogen atmosphere. I do.
特に、５００℃からの昇温速度を１００〜４００℃／ｈとし、１１５０〜１２６０℃の温度で焼成することにより、被覆された希土類元素、Ｍｇ、Ｍｎが、主結晶粒子中により中央部側まで存在するようになるとともに、アルカリ土類元素、希土類元素およびＳｉを含有する複合酸化物を粒界相に存在させるとともに、Ａｌが主結晶粒子中への進入を防ぎ、粒界相に存在させることができる。 In particular, the heating rate from 500 ° C. is set to 100 to 400 ° C./h, and firing is performed at a temperature of 1150 to 1260 ° C., so that the coated rare earth element, Mg, and Mn can reach the central portion side in the main crystal particles. In addition to the presence of alkaline earth elements, rare earth elements and Si-containing composite oxides in the grain boundary phase, Al prevents entry into the main crystal grains and exists in the grain boundary phase. Can do.
これはＢａＴｉＯ３粉の表面に希土類元素、ＭｇおよびＭｎを被覆しているため、これらの希土類元素、ＭｇおよびＭｎのＢａＴｉＯ３粉末へ固溶し易くなり、ＢａＴｉＯ３内部まで全体に存在するようになるが、そのうちＭｇおよびＭｎが優先的にＢａＴｉＯ３粉末へ固溶していくため、被覆している希土類元素のうち一部がＢａＴｉＯ３粉末に固溶しきれず、ＢａＴｉＯ３表面に取り残され、上記したような、５００℃から焼結温度までの昇温速度を従来よりも低い１００〜４００℃／ｈとすることにより、添加物成分として添加したＣａＯ、ＳｉＯ２と反応し、アルカリ土類元素、希土類元素およびＳｉとの複合酸化物、例えばＣａ４Ｙ６Ｏ（ＳｉＯ４）結晶相からなる被覆層が主結晶粒子表面に生成すると考えている。 This is because the surface of the BaTiO 3 powder is coated with rare earth elements, Mg and Mn, so that it easily dissolves in the BaTiO 3 powder of these rare earth elements, Mg and Mn, so that the entire surface of the BaTiO 3 exists. made, but because of which Mg and Mn is gradually dissolved into preferentially BaTiO 3 powder, a portion of the rare earth element is coated is not completely dissolved in the BaTiO 3 powder, stranded on BaTiO 3 surface, the The heating rate from 500 ° C. to the sintering temperature is set to 100 to 400 ° C./h, which is lower than the conventional one, so that it reacts with CaO and SiO 2 added as additive components, and alkaline earth elements, It is considered that a coating layer composed of a complex oxide of a rare earth element and Si, for example, a Ca 4 Y 6 O (SiO 4 ) crystal phase is formed on the surface of the main crystal particle.
この後、焼成した電子部品本体をボールミルにてバレル研磨し、その両端面に、外部電極ペーストを塗布して窒素中で焼き付けることによって外部電極を形成する。さらに外部電極の表面を脱脂、酸洗浄、純水を用いた水洗を行った後、バレル方式により、メッキを行う。 Thereafter, the fired electronic component main body is barrel-polished by a ball mill, and an external electrode paste is applied to both end faces thereof and baked in nitrogen to form external electrodes. Further, the surface of the external electrode is degreased, acid washed, and washed with pure water, and then plated by a barrel method.
本発明では金属元素として、少なくともＢａ、Ｔｉ、希土類元素、ＭｇおよびＭｎを含有するペロブスカイト型複合酸化物である主結晶粒子と、粒界相とからなり、主結晶粒子の内部に存在するＡｌ元素が酸化物換算で０．０１重量％以下であるとともに、粒界相に平均して０．０５〜２．０質量％の割合でＡｌ元素を含有することにより、結晶粒子を微細化しても高い比誘電率を維持し、チッピングを防止できるまた、主結晶粒子表面にはアルカリ土類元素、希土類元素およびＳｉを含有する複合酸化物からなる被覆層が形成されており、該被覆層がＭ４Ｒ６Ｏ（ＳｉＯ４）型構造（Ｍはアルカリ土類元素、Ｒは希土類元素）を有することにより、薄層化しても誘電体磁器の絶縁破壊電圧を向上できる。主結晶粒子の一部あるいは全部のＢａ元素が３０原子％以下の比率でＣａ元素に置き換えることもできる。 In the present invention, an Al element which is composed of a main crystal particle which is a perovskite complex oxide containing at least Ba, Ti, rare earth element, Mg and Mn as a metal element, and a grain boundary phase, and is present inside the main crystal particle. Is 0.01% by weight or less in terms of oxide, and it is high even if the crystal grains are refined by containing Al element in a proportion of 0.05 to 2.0% by mass on the average in the grain boundary phase. maintaining the specific permittivity, and can prevent chipping, the main crystal on the particle surface alkaline earth elements, and the coating layer made of a complex oxide containing a rare earth element and Si is formed, the coating layer is M 4 By having an R 6 O (SiO 4 ) type structure (M is an alkaline earth element and R is a rare earth element), the dielectric breakdown voltage of the dielectric ceramic can be improved even if the layer is thinned. Some or all of the main crystal grains may be replaced with Ca elements at a ratio of 30 atomic% or less.
積層型電子部品の一つである積層セラミックコンデンサを以下のようにして作製した。まず、誘電体素材料として、比表面積平均粒径が２．５μｍのＢａＴｉＯ３粉末を用い、このＢａＴｉＯ３粉末１００重量部に対して、ＭｇＯを０．２モル部、ＭｎＣＯ３を０．１モル部と、Ｙ２Ｏ３、Ｄｙ２Ｏ３、およびＨｏ２Ｏ３のうちのいずれか１種類０．５ｍｏｌ部とを、Ｍｇ、Ｍｎ、Ｙ等が混在した状態で存在するように被覆し、この被覆ＢａＴｉＯ３粉に対して、Ａｌ２Ｏ３を１質量％含有するＬｉ２ＯおよびＳｉＯ２と、ＣａＯからなる添加物成分を、被覆ＢａＴｉＯ３粉１００質量部に対して、１質量部添加し、直径５ｍｍのＺｒＯ２ボールを用いたボールミルにて湿式粉砕することにより調製した。 A multilayer ceramic capacitor, which is one of the multilayer electronic components, was produced as follows. First, BaTiO 3 powder having a specific surface area average particle size of 2.5 μm is used as a dielectric material, and 0.2 mol part of MgO and 0.1 mol of MnCO 3 are added to 100 parts by weight of this BaTiO 3 powder. And 0.5 mol part of any one of Y 2 O 3 , Dy 2 O 3 , and Ho 2 O 3 are coated so as to exist in a mixed state of Mg, Mn, Y, etc. for this coating BaTiO 3 powder, and Li 2 O and SiO 2 containing Al 2 O 3 1% by weight, the additive component consisting of CaO, based on coating BaTiO 3 powder 100 parts by weight 1 part by weight additive Then, it was prepared by wet grinding with a ball mill using ZrO 2 balls having a diameter of 5 mm.
次に、この粉末に有機バインダを混合してスラリーを調製し、ドクターブレードによりグリーンシートを作製した。その厚みは３．０μｍである。 Next, an organic binder was mixed with this powder to prepare a slurry, and a green sheet was produced with a doctor blade. Its thickness is 3.0 μm.
次にこのグリーンシート上に、Ｎｉを主成分とする内部電極ペーストをスクリーン印刷した。 Next, an internal electrode paste containing Ni as a main component was screen-printed on the green sheet.
次に、内部電極ペーストを印刷したグリーンシートを１００枚積層し、その上下面に、内部電極ペーストを印刷していないグリーンシートをそれぞれ２０枚積層し、プレス機を用いて一体化し、積層成形体を得た。 Next, 100 green sheets on which internal electrode paste was printed were laminated, and 20 green sheets on which no internal electrode paste was printed were laminated on the upper and lower surfaces thereof, and were integrated using a press machine. Got.
この後、積層成形体を格子状に切断して、２．３ｍｍ×１．５ｍｍ×０．５ｍｍの電子部品本体の成形体を作製した。 Thereafter, the laminated molded body was cut into a lattice shape to produce a molded body of an electronic component main body of 2.3 mm × 1.5 mm × 0.5 mm.
次に、この電子部品本体の成形体を１０℃／ｈの昇温速度で大気中で２５０℃／ｈにて脱バインダー処理を行い、５００℃からの昇温速度が１５０℃／ｈの昇温速度で、１１５０℃〜１２５０℃（酸素分圧１０−１１ａｔｍ）で２時間焼成し、続いて１５０℃／ｈの降温速度で１０００℃まで冷却し、窒素雰囲気中１０００℃で４時間再酸化処理をし、１５０℃／ｈの降温速度で冷却し、電子部品本体を作製した。この内部電極層５の有効面積は２．１ｍｍ２であった。また、誘電体層の厚みは２．３μｍであった。また、誘電体粉末として、ＢａＴｉＯ３のＢａサイトをＣａで１０モル％置換したものも同様に作製した。 Next, the molded body of the electronic component main body was debindered at 250 ° C./h in the air at a temperature increase rate of 10 ° C./h, and the temperature increase rate from 500 ° C. was 150 ° C./h. Baked at a rate of 1150 ° C. to 1250 ° C. (oxygen partial pressure 10 −11 atm) for 2 hours, subsequently cooled to 1000 ° C. at a rate of 150 ° C./h, and reoxidized at 1000 ° C. for 4 hours in a nitrogen atmosphere. The electronic component main body was manufactured by cooling at a cooling rate of 150 ° C./h. The effective area of the internal electrode layer 5 was 2.1 mm 2 . The thickness of the dielectric layer was 2.3 μm. In addition, a dielectric powder in which the Ba site of BaTiO 3 was substituted with 10 mol% of Ca was similarly produced.
比較例として、被覆のないＢａＴｉＯ３１００モル部に対して、粉末状のＭｇＯを０．２モル部、ＭｎＣＯ３を０．１モル部と、表１に示す割合の、Ｙ２Ｏ３を加え、さらにこれらの混合物１００重量部に対して、Ｌｉ２ＯとＳｉＯ２とＢａＯおよびＡｌ２Ｏ３からなる低融点ガラス成分(それぞれ２０モル％、５０モル％、２０モル％、１０ｍｏｌ％)を１重量部加えた組成物を湿式調製して、厚み３．０μｍのグリーンシートを作製した。この比較例となる試料についても上記した積層、焼成工程を経て作製した。 As a comparative example, with respect to BaTiO 3 100 molar parts uncoated, 0.2 molar parts of powdered MgO, and 0.1 mole part of MnCO 3, in the proportions shown in Table 1, the Y 2 O 3 was added Further, a low-melting glass component composed of Li 2 O, SiO 2 , BaO, and Al 2 O 3 (20 mol%, 50 mol%, 20 mol%, 10 mol%, respectively) is 1 per 100 parts by weight of the mixture. The composition added with parts by weight was wet prepared to produce a green sheet having a thickness of 3.0 μm. This sample as a comparative example was also manufactured through the above-described lamination and firing steps.
次に、焼成した電子部品本体をバレル研磨した後、電子部品本体の両端部にＣｕ粉末とガラスを含んだ外部電極ペーストを塗布し、８５０℃、窒素中で焼き付けを行い外部電極を形成した。その後、電解バレル機を用いて、この外部電極の表面に、順にＮｉメッキおよびＳｎメッキを行い、積層セラミックコンデンサを作製した。 Next, the fired electronic component body was barrel-polished, and then an external electrode paste containing Cu powder and glass was applied to both ends of the electronic component body, followed by baking in nitrogen at 850 ° C. to form external electrodes. Thereafter, using an electrolytic barrel machine, Ni plating and Sn plating were sequentially performed on the surface of the external electrode to produce a multilayer ceramic capacitor.
次に、これらの積層セラミックコンデンサの比誘電率、絶縁耐圧、静電容量の温度特性の測定を行った。比誘電率及び静電容量の温度特性は周波数１．０ｋＨｚ、測定電圧０．５Ｖｒｍｓの測定条件で、また絶縁耐圧は、リーク電流が０．５Ａに達したときの電圧を測定した。また、バレル研磨時に１００個あたり発生したチッピングの個数を表１に記載した。また、比誘電率は、静電容量と内部電極層の有効面積、誘電体層の厚みから算出した。主結晶粒子の平均粒径は断面の電子顕微鏡観察よりインターセプト法により求めた。結晶粒子のｃ／ａはＸ線回折により求めた。結果を表１に記載する。 Next, the relative dielectric constant, withstand voltage, and capacitance temperature characteristics of these multilayer ceramic capacitors were measured. The temperature characteristics of the dielectric constant and capacitance were measured under the conditions of a frequency of 1.0 kHz and a measurement voltage of 0.5 Vrms, and the withstand voltage was measured when the leakage current reached 0.5 A. In addition, Table 1 shows the number of chippings generated per 100 during barrel polishing. The relative dielectric constant was calculated from the capacitance, the effective area of the internal electrode layer, and the thickness of the dielectric layer. The average particle size of the main crystal particles was determined by the intercept method from observation of the cross section by an electron microscope. The c / a of the crystal particles was determined by X-ray diffraction. The results are listed in Table 1.
尚、誘電体層中の被覆層の評価は、電子顕微鏡観察およびＥＤＳ測定と微小領域電子線回折法により行った。主結晶粒子内および粒界層中のＡｌ量は透過電子顕微鏡観察およびＥＤＳ測定により算出した。
表１の結果から明らかなように、本発明にかかる試料Ｎｏ．１、３、５〜７では、比誘電率が２０５０以上、静電容量の温度依存性が−１０〜０％の範囲内、絶縁耐圧が２１０Ｖ以上でチッピングが無かった。また、本発明の試料では、いずれも主結晶粒子の平均粒径は０．４μｍ以下、結晶粒子のｃ／ａは１．００５以上であった。 As is apparent from the results in Table 1, the sample No. In 1, 3, 5-7, the relative dielectric constant was 2050 or more, the temperature dependency of capacitance was in the range of -10 to 0%, the withstand voltage was 210 V or more, and there was no chipping. In all the samples of the present invention, the average particle size of the main crystal particles was 0.4 μm or less, and the c / a of the crystal particles was 1.005 or more.
一方、粒界層のＡｌ含有量が本発明の範囲に満たない場合、バレル研磨時に多くのチッピングが発生し、粒内において本発明の範囲よりもＡｌ含有量が多いと温度特性が大きくなった。 On the other hand, when the Al content in the grain boundary layer is less than the range of the present invention, a lot of chipping occurred during barrel polishing, and the temperature characteristics increased when the Al content in the grain was larger than the range of the present invention. .
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