JP2007119275A - Dielectric ceramic - Google Patents
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本発明は、誘電体磁器に関し、特に、温度補償用の積層セラミックコンデンサに用いる誘電体磁器に関するものである。 The present invention relates to a dielectric ceramic, and more particularly to a dielectric ceramic used for a temperature compensation multilayer ceramic capacitor.
近年、高容量タイプの積層セラミックコンデンサは内部電極に卑金属を採用し、誘電体磁器は耐還元性を持たせたものが開発されているが、このような高容量タイプの積層セラミックコンデンサと同様、温度補償用のコンデンサにおいても、それに用いる誘電体磁器もまた高積層および低コスト化のために誘電体磁器の高誘電率化が図られている（例えば、特許文献１）。
しかしながら、上記特許文献１に開示された誘電体磁器では、比誘電率が高々２６０程度であり、依然として比誘電率は低いものであった。 However, the dielectric ceramic disclosed in Patent Document 1 has a relative dielectric constant of about 260 at most, and the relative dielectric constant is still low.
従って本発明は、温度補償用のコンデンサに採用可能な高誘電率の誘電体磁器を提供することを目的とするものである。 Accordingly, an object of the present invention is to provide a dielectric ceramic having a high dielectric constant that can be used in a capacitor for temperature compensation.
本発明の誘電体磁器は、（１）Ｂａ、Ｓｒ、Ｃａ、ＴｉおよびＺｒをそれぞれ酸化物として含有する主結晶粒子により形成された誘電体磁器であって、
前記Ｂａ、Ｓｒ、Ｃａ、ＴｉおよびＺｒが、
Ｂａ＝０．４５〜１．０１、
Ｓｒ＝０〜０．５、
Ｃａ＝０〜０．０５、
Ｔｉ＝０．４〜０．６、
Ｚｒ＝０．４〜０．６
のモル比であるとともに、
ＴｉおよびＺｒの合量モル数を１としたときに、Ｂａ、ＳｒおよびＣａの合量のモル数ｍが０．９９５〜１．０１の範囲であり、かつ、
Ｚｒ／Ｔｉ比がモル比で０．６〜１．５の範囲であることを特徴とする。
The dielectric ceramic according to the present invention is (1) a dielectric ceramic formed of main crystal particles each containing Ba, Sr, Ca, Ti and Zr as oxides,
Ba, Sr, Ca, Ti and Zr are
Ba = 0.45 to 1.01,
Sr = 0-0.5,
Ca = 0-0.05,
Ti = 0.4-0.6,
Zr = 0.4-0.6
As well as the molar ratio of
When the total molar number of Ti and Zr is 1, the total molar number m of Ba, Sr and Ca is in the range of 0.995 to 1.01, and
The Zr / Ti ratio is in the range of 0.6 to 1.5 in terms of molar ratio.
また上記誘電体磁器では、（２）前記主結晶粒子の平均粒径が０．５μｍ以下であること、（３）前記主結晶粒子の表面から５ｎｍの領域での平均カルシウム濃度をＣ５とし、粒子中心部におけるカルシウムの濃度をＣＣとした時、ＣＣ／Ｃ５≦０．７を満足することが望ましい。 In the dielectric ceramic, (2) the average particle size of the main crystal particles is 0.5 μm or less, and (3) the average calcium concentration in a region 5 nm from the surface of the main crystal particles is C 5 , When the calcium concentration at the center of the particle is C C , it is desirable to satisfy C C / C 5 ≦ 0.7.
本発明によれば、Ｂａ、Ｓｒ、Ｃａ、ＴｉおよびＺｒをそれぞれ酸化物として含有する主結晶粒子により形成された誘電体磁器について、その組成を上記の範囲とすることにより、温度補償用のコンデンサに採用可能であり、しかも高い比誘電率を示す誘電体磁器を得ることができる。 According to the present invention, with respect to a dielectric ceramic formed of main crystal grains each containing Ba, Sr, Ca, Ti and Zr as oxides, by setting the composition within the above range, a capacitor for temperature compensation In addition, it is possible to obtain a dielectric ceramic exhibiting a high relative dielectric constant.
特に本発明では、誘電体磁器に含まれるＺｒ／Ｔｉ比をモル比で０．６〜１．５の範囲とすることで、強誘電体の常誘電相−強誘電相の相転移温度を使用温度領域より低温度にシフトさせることができ、これにより室温を含む使用温度域において高い誘電率となり低損失かつ比誘電率の温度係数が低い常誘電的性質を利用した誘電体磁器を提供することができる。 In particular, in the present invention, the phase transition temperature of the paraelectric phase to the ferroelectric phase of the ferroelectric is used by setting the molar ratio of Zr / Ti contained in the dielectric ceramic to be in the range of 0.6 to 1.5. To provide a dielectric ceramic using a paraelectric property that can be shifted to a lower temperature than the temperature range, thereby having a high dielectric constant in a use temperature range including room temperature, a low loss, and a low temperature coefficient of relative dielectric constant. Can do.
本発明の誘電体磁器は、Ｂａ、Ｓｒ、Ｃａ、ＴｉおよびＺｒをそれぞれ酸化物として含有する主結晶粒子により形成されたことを特徴とする。 The dielectric ceramic according to the present invention is characterized in that it is formed of main crystal grains each containing Ba, Sr, Ca, Ti and Zr as oxides.
ここで、Ｂａ量が０．４５〜１．０１モルの範囲である。Ｂａが０．４５モル以上であると比誘電率が高くなるという利点がある。一方、Ｂａが１．０１モル以下であると比誘電率の温度係数を小さくできるという利点がある。 Here, the amount of Ba is in the range of 0.45 to 1.01 mol. When Ba is 0.45 mol or more, there is an advantage that the relative dielectric constant is increased. On the other hand, when Ba is 1.01 mol or less, there is an advantage that the temperature coefficient of relative permittivity can be reduced.
Ｓｒ量は０〜０．５モルの範囲である。Ｓｒが０．５モル以下であると比誘電率が高くなるという利点がある。 The amount of Sr is in the range of 0 to 0.5 mol. When Sr is 0.5 mol or less, there is an advantage that the relative dielectric constant is increased.
Ｃａ量は０〜０．１モルである。Ｃａが０．１モル以下であると比誘電率の温度係数を小さくできるという利点がある。 The amount of Ca is 0 to 0.1 mol. There exists an advantage that the temperature coefficient of a dielectric constant can be made small as Ca is 0.1 mol or less.
Ｔｉ量およびＺｒ量はともに０．４〜０．６モルであることが重要である。つまり、ＴｉおよびＺｒ量が上記のモル量であり、Ｚｒ／Ｔｉ比がモル比で０．６〜１．５の範囲であれば、Ｂａ、Ｓｒ、Ｃａ、ＴｉおよびＺｒの複合酸化物から形成されるペロブスカイト構造を有する誘電体について、強誘電体の常誘電相−強誘電相の相転移温度を使用温度領域より低温度にシフトさせることができ、これにより常誘電相−強誘電相の相転移温度が室温を中心とした使用温度から離れて、相転移に伴う比誘電率の温度変化の影響が小さくなり、誘電体の比誘電率の温度変化率を小さいものにできる。 It is important that both the Ti amount and the Zr amount are 0.4 to 0.6 mol. That is, when the Ti and Zr amounts are the above molar amounts and the Zr / Ti ratio is in the range of 0.6 to 1.5 in terms of molar ratio, it is formed from a composite oxide of Ba, Sr, Ca, Ti and Zr. As for the dielectric having a perovskite structure, the phase transition temperature of the ferroelectric paraelectric phase to the ferroelectric phase can be shifted to a temperature lower than the operating temperature range, whereby the phase of the paraelectric phase to the ferroelectric phase can be changed. Since the transition temperature is far from the use temperature centering on room temperature, the influence of the temperature change of the relative dielectric constant accompanying the phase transition is reduced, and the temperature change rate of the dielectric constant of the dielectric can be reduced.
また、上記Ｂａ、Ｓｒ、Ｃａ、ＴｉおよびＺｒを含む組成系において、ＴｉおよびＺｒの合量モル数を１としたときに、Ｂａ、ＳｒおよびＣａの合量のモル数ｍが０．９９５〜１．０１の範囲であることが重要である。Ｂａ、Ｓｒ、Ｃａ、ＴｉおよびＺｒを含む組成を上記ｍの関係とすることで、これらの元素の酸化物から形成される主結晶粒子をより純粋なペロブスカイト構造を有する誘電体が形成され、これにより高い比誘電率を得ることができる。 In the composition system containing Ba, Sr, Ca, Ti and Zr, when the total molar number of Ti and Zr is 1, the total molar number m of Ba, Sr and Ca is 0.995 to It is important that it is in the range of 1.01. By setting the composition containing Ba, Sr, Ca, Ti and Zr to the relationship of m above, a dielectric having a purer perovskite structure is formed from the main crystal particles formed from oxides of these elements. A higher relative dielectric constant can be obtained.
Ｂａ量が０．４５モルよりも少ないと焼結性が低下し誘電体磁器の比誘電率が低いものとなる。またＢａ量が１．０１モルよりも多いと比誘電率は高くなるものの比誘電率の温度変化率が大きくなる。 If the amount of Ba is less than 0.45 mol, the sinterability is lowered and the dielectric constant of the dielectric ceramic is low. On the other hand, if the amount of Ba is more than 1.01 mol, the relative dielectric constant increases, but the temperature change rate of the relative dielectric constant increases.
Ｓｒ量が０．５モルよりも多くなる場合、またはＣａ量が０．１よりも多い場合には比誘電率が低下する。また、Ｃａ量が０．１モルよりも多い場合には、主結晶粒子の合成が困難となり、特にＴｉサイトをイオン半径の大きなＺｒで置換した本発明のような材料においては、イオン半径の小さいＣａでＢａを置換すると結晶格子が不安定になるため固溶が困難となる。 When the Sr amount is more than 0.5 mol, or when the Ca amount is more than 0.1, the relative dielectric constant is lowered. In addition, when the amount of Ca is more than 0.1 mol, it becomes difficult to synthesize main crystal particles. In particular, in a material such as the present invention in which Ti sites are substituted with Zr having a large ionic radius, the ionic radius is small. When Ba is substituted with Ca, the crystal lattice becomes unstable, so that solid solution becomes difficult.
Ｔｉ量が０．４モルよりも少なく、Ｚｒ量が０．６モルよりも多い場合には焼結性が低下し緻密な磁器を得ることが困難となり、一方、Ｔｉ量が０．６モルよりも多く、Ｚｒ量が０．４モルよりも少ない場合には比誘電率の温度変化率が大きくなる。 When the Ti amount is less than 0.4 mol and the Zr amount is more than 0.6 mol, the sinterability is lowered and it becomes difficult to obtain a dense porcelain, while the Ti amount is less than 0.6 mol. When the amount of Zr is less than 0.4 mol, the temperature change rate of the relative permittivity increases.
結果的に、Ｚｒ／Ｔｉ比がモル比で０．６〜１．５の範囲を逸脱する場合には、強誘電体の常誘電相−強誘電相の相転移温度を使用温度領域より低温度にシフトさせることが困難となり、常誘電相−強誘電相の相転移温度が室温を中心とした使用温度に近い場合は、相転移に伴う比誘電率の温度変化により比誘電率の温度変化率が大きくなる。 As a result, when the Zr / Ti ratio is out of the range of 0.6 to 1.5 in terms of molar ratio, the phase transition temperature of the ferroelectric paraelectric phase to the ferroelectric phase is lower than the operating temperature range. When the phase transition temperature between the paraelectric phase and the ferroelectric phase is close to the operating temperature centered on room temperature, the temperature change rate of the relative permittivity due to the temperature change of the relative permittivity accompanying the phase transition Becomes larger.
即ち、本発明の誘電体磁器は以下の組成式で示されるものである。つまり、主結晶粒子の組成を（Ｂａ１−ｘ−ｙＳｒｘＣａｙ）ｍ（Ｔｉ１−ｚＺｒｚ）Ｏ３と表した時、各構成元素の組成範囲が、０≦ｘ≦０．５、０＜ｙ＜０．１０、０．４≦ｚ≦０．６、０．９９５≦ｍ≦１．０１０である。ここで、ｍの値を０．９９５〜１．０１０とすると、異相なしに安定的に所望の磁器構造を実現することができ、比誘電率を高めかつ誘電損失を低くできるという利点がある。 That is, the dielectric ceramic of the present invention is represented by the following composition formula. That is, when the composition of the main crystal particles is expressed as (Ba 1-xy Sr x Ca y ) m (Ti 1-z Zr z ) O 3 , the composition range of each constituent element is 0 ≦ x ≦ 0. 5, 0 <y <0.10, 0.4 ≦ z ≦ 0.6, 0.995 ≦ m ≦ 1.010. Here, if the value of m is 0.995 to 1.010, there is an advantage that a desired porcelain structure can be stably realized without different phases, and the relative permittivity can be increased and the dielectric loss can be reduced.
本発明の誘電体磁器では、転移温度を低温度にシフトさせる上でＺｒ量、Ｓｒ量、Ｃａ量の調整が必要であり、特に、Ｔｉ量に対するＺｒ量を調整することが重要である。 In the dielectric ceramic according to the present invention, it is necessary to adjust the amount of Zr, the amount of Sr, and the amount of Ca in order to shift the transition temperature to a low temperature. In particular, it is important to adjust the amount of Zr with respect to the amount of Ti.
通常、温度補償用の誘電体磁器としては強誘電性を抑制させる必要があるが、本発明においては、強誘電体の常誘電相−強誘電相の相転移温度を使用温度領域より低温度にシフトさせることにより、室温を含む使用温度域において現れる常誘電的性質が大きくなる。このため比誘電率の温度変化率が抑制されて、比誘電率が高く、誘電損失の低い誘電体磁器を得ることができる。 Usually, it is necessary to suppress ferroelectricity as a dielectric ceramic for temperature compensation. However, in the present invention, the phase transition temperature of the ferroelectric paraelectric phase to the ferroelectric phase is set lower than the operating temperature range. By shifting, the paraelectric property appearing in the use temperature range including room temperature is increased. For this reason, the temperature change rate of the relative permittivity is suppressed, and a dielectric ceramic having a high relative permittivity and a low dielectric loss can be obtained.
また、上記誘電体磁器では、主結晶粒子の平均粒径が０．５μｍ以下であることが望ましい。主結晶粒子の平均粒径が０．５μｍ以下であると比誘電率の温度変化率を低減できるという利点がある。 In the dielectric ceramic, it is desirable that the average grain size of the main crystal particles is 0.5 μm or less. When the average particle size of the main crystal particles is 0.5 μm or less, there is an advantage that the temperature change rate of the relative dielectric constant can be reduced.
また、本発明の誘電体磁器は主結晶粒子の表面から５ｎｍの領域での平均カルシウム濃度をＣ５とし、粒子中心部におけるカルシウムの濃度をＣＣとした時、ＣＣ／Ｃ５≦０．７を満足することが望ましい。 In the dielectric ceramic according to the present invention, when the average calcium concentration in the region 5 nm from the surface of the main crystal particle is C 5 and the calcium concentration in the center of the particle is C C , C C / C 5 ≦ 0. It is desirable to satisfy 7.
通常、上記Ｂａ、Ｓｒ、Ｃａ、ＴｉおよびＺｒを含む組成の誘電体磁器においてＣａ量が多いと高温負荷寿命の信頼性が高くかつ比誘電率の温度変化率も小さいものとなるが、これに加えて、本発明では、特に、主結晶粒子の表面付近にＣａを偏在させて粒界近傍でのＣａの固溶量を増大することで、比誘電率が高く、かつ高温負荷寿命の信頼性が高く、比誘電率の温度変化率の小さい誘電体磁器を実現する。 Usually, in a dielectric ceramic having a composition containing Ba, Sr, Ca, Ti and Zr, if the amount of Ca is large, the reliability of the high temperature load life is high and the temperature change rate of the relative dielectric constant is small. In addition, in the present invention, in particular, the Ca is unevenly distributed in the vicinity of the surface of the main crystal grains to increase the solid solution amount of Ca in the vicinity of the grain boundary, so that the relative dielectric constant is high and the reliability of the high temperature load life is increased. This realizes a dielectric ceramic having a high relative dielectric constant and a small temperature change rate of relative permittivity.
また、一般に、ペロブスカイト型酸化物材料においては、非酸化性の雰囲気において焼成を行うと酸素欠陥を生じやすく絶縁性と高温負荷寿命の信頼性が低下するが、ＢａサイトをＣａで置換し、上記のようにＣａを主結晶粒子の表面付近に偏在させることで、酸素欠陥を補償でき、高温負荷寿命の信頼性を向上できる。 In general, in the perovskite type oxide material, if baked in a non-oxidizing atmosphere, oxygen defects are likely to occur, and the reliability of insulation and high temperature load life is reduced. However, the Ba site is replaced with Ca, As described above, Ca is unevenly distributed in the vicinity of the surface of the main crystal grains, whereby oxygen defects can be compensated for and the reliability of the high temperature load life can be improved.
次に、本発明の誘電体磁器の製法について説明する。本発明の誘電体磁器は、組成が（Ｂａ１−ｘ−ｙＳｒｘＣａｙ）ｍ（Ｔｉ１−ｚＺｒｚ）Ｏ３と表した時、各構成元素の組成範囲が、０≦ｘ≦０．５、０＜ｙ＜０．１０、０．４≦ｚ≦０．６、０．９９５≦ｍ≦１．０１０の範囲にある誘電体粉末を主成分粉末（ＢＳＣＴＺ粉末）として用いるものである。この主成分粉末の平均粒径は０．５μｍ以下、特に０．４μｍ以下が好ましい。主成分粉末の平均粒径が０．５μｍ以下であると、焼結後の主結晶粒子の平均粒径を０．５μｍ以下にできるために、誘電体磁器の比誘電率の温度変化率を小さくできるという利点がある。一方、主成分粉末の平均粒径は０．２μｍ以上であると、焼結後に形成される主結晶粒子が結晶性の高いものとなり、そのために誘電体磁器の比誘電率を高めることができるという利点がある。 Next, a method for manufacturing the dielectric ceramic according to the present invention will be described. When the composition of the dielectric ceramic according to the present invention is expressed as (Ba 1-xy Sr x Ca y ) m (Ti 1-z Zr z ) O 3 , the composition range of each constituent element is 0 ≦ x ≦ A dielectric powder in the range of 0.5, 0 <y <0.10, 0.4 ≦ z ≦ 0.6, 0.995 ≦ m ≦ 1.010 is used as the main component powder (BSCTZ powder). is there. The average particle size of the main component powder is preferably 0.5 μm or less, particularly preferably 0.4 μm or less. If the average particle size of the main component powder is 0.5 μm or less, the average particle size of the sintered main crystal particles can be 0.5 μm or less, so the temperature change rate of the dielectric constant of the dielectric ceramic is reduced. There is an advantage that you can. On the other hand, when the average particle size of the main component powder is 0.2 μm or more, the main crystal particles formed after sintering have high crystallinity, and therefore the dielectric constant of the dielectric ceramic can be increased. There are advantages.
次に、上記主成分粉末に対して組成式Ｂａ１−ｐＣａｐＴｉＯ３（ｐ＝０．０１〜０．１）で表される副成分粉末（ＢＣＴ粉末）を所定量添加する。この副成分粉末の平均粒径は０．０２μｍ以上０．１μｍ以下、特に０．０３μｍ以上０．０８μｍ以下であることが好ましい。副成分粉末の平均粒径が０．１μｍ以下であると主成分粉末の表面に均一に分散しやすくなり、これにより主成分粉末の表面付近のＣａ濃度を高めやすくなり、焼結後は主結晶粒子の表面付近にＣａを偏在させやすくなる。主成分粉末の平均粒径が０．２μｍ以上であると焼成時の異常粒成長を抑制できるという利点がある。また、この副成分粉末の添加量は主成分粉末１００質量部に対して０．３〜１．２質量部が好ましい。 Then it added a predetermined amount of the secondary component powder (BCT powder) represented by the above-mentioned main components powder relative composition formula Ba 1-p Ca p TiO 3 (p = 0.01~0.1). The average particle size of the subcomponent powder is preferably 0.02 μm or more and 0.1 μm or less, and particularly preferably 0.03 μm or more and 0.08 μm or less. If the average particle size of the subcomponent powder is 0.1 μm or less, it becomes easy to uniformly disperse on the surface of the main component powder, which makes it easy to increase the Ca concentration near the surface of the main component powder, and after sintering, the main crystal Ca tends to be unevenly distributed near the surface of the particle. When the average particle size of the main component powder is 0.2 μm or more, there is an advantage that abnormal particle growth during firing can be suppressed. Moreover, the addition amount of the subcomponent powder is preferably 0.3 to 1.2 parts by mass with respect to 100 parts by mass of the main component powder.
副成分粉末の添加量は主成分粉末１００質量部に対して０．３質量部以上であると、主結晶粒子の焼結性を高めることができるとともに主結晶粒子の表面付近におけるＣａ濃度を高めることができるという利点がある。一方、副成分粉末の添加量は主成分粉末１００質量部に対して１質量部以下であると、誘電体磁器の比誘電率を高めることができるという利点がある。 When the added amount of the subcomponent powder is 0.3 parts by mass or more with respect to 100 parts by mass of the main component powder, the sinterability of the main crystal particles can be enhanced and the Ca concentration near the surface of the main crystal particles is increased. There is an advantage that you can. On the other hand, when the added amount of the subcomponent powder is 1 part by mass or less with respect to 100 parts by mass of the main component powder, there is an advantage that the dielectric constant of the dielectric ceramic can be increased.
ここで用いる主成分粉末および副成分粉末は、固相法、液相法（蓚酸塩を介して生成する方法を含む）、水熱合成法、気相法などから選ばれる合成法により得られたものである。前記製法のなかで特に原料単価が安く、合成方法も仮焼手段が取れ、多量に生産でき、得られる誘電体粉末の結晶性が高く、焼結性が高いという理由から固相法により得られた誘電体粉末がより望ましい。 The main component powder and subcomponent powder used here were obtained by a synthesis method selected from a solid phase method, a liquid phase method (including a method of forming via oxalate), a hydrothermal synthesis method, a gas phase method, and the like. Is. Among the above-mentioned production methods, the raw material unit price is particularly low, the synthesis method can also be obtained by calcining means, can be produced in large quantities, and the dielectric powder obtained has high crystallinity and high sinterability. A dielectric powder is more desirable.
次に、本発明の誘電体磁器を形成する場合、上記主成分粉末および副成分粉末に対して所定量の添加物を添加する。添加物としてはＭｇ、Ｍｎ、希土類元素が好ましく、Ｍｇ、希土類元素およびＭｎの酸化物は誘電体磁器における主結晶粒子の粒成長の制御および絶縁性を高めるという効果があり、Ｍｎの酸化物はまた耐還元性を高められる。希土類元素としては、例えば、Ｙ、Ｄｙ、Ｅｒ、Ｈｏ等が選択され、Ｙは比誘電率を高める効果がある。 Next, when forming the dielectric ceramic of the present invention, a predetermined amount of additives is added to the main component powder and subcomponent powder. As additives, Mg, Mn, and rare earth elements are preferable, and oxides of Mg, rare earth elements, and Mn have the effect of controlling the grain growth of the main crystal grains in the dielectric ceramic and improving the insulation properties. Moreover, reduction resistance can be improved. For example, Y, Dy, Er, Ho or the like is selected as the rare earth element, and Y has an effect of increasing the relative dielectric constant.
Ｍｇ、Ｍｎ、希土類元素のそれぞれの酸化物（Ｍｎは炭酸化合物）の添加量は主成分粉末１００質量部に対して、ＭｇはＭｇＯ換算で０．０４〜０．１４質量部、ＭｎはＭｎＣＯ３換算で０．０４〜０．３質量部、希土類元素の酸化物は０．１〜１．５質量部であることが望ましい。これらＭｇ、Ｍｎ、希土類元素のそれぞれの酸化物の平均粒径は０．０１μｍ以上０．１μｍ以下であることがこれら添加物粉末の分散性を高めるという点で好ましい。 The added amount of each of Mg, Mn, and rare earth element oxide (Mn is a carbonic acid compound) is 100 parts by mass of the main component powder, Mg is 0.04 to 0.14 parts by mass in terms of MgO, and Mn is MnCO 3. It is desirable that 0.04 to 0.3 parts by mass in terms of conversion and 0.1 to 1.5 parts by mass of the rare earth element oxide. The average particle size of the respective oxides of Mg, Mn, and rare earth elements is preferably 0.01 μm or more and 0.1 μm or less from the viewpoint of improving the dispersibility of these additive powders.
次に、上記主成分粉末（ＢＳＣＴＺ粉末）に対して副成分粉末（ＢＣＴ粉末）、ならびにＭｇ，Ｍｎ希土類元素のそれぞれの酸化物などの添加物を混合した混合粉末を所定の形状に成形し、この成形体を、所定の雰囲気下、温度条件で焼成して誘電体磁器が形成される。 Next, a mixed powder obtained by mixing additives such as subcomponent powder (BCT powder) and Mg, Mn rare earth elements with respect to the main component powder (BSCTZ powder) is formed into a predetermined shape, The molded body is fired under a predetermined atmosphere at a temperature condition to form a dielectric ceramic.
焼成温度は最高温度が１２００〜１４００℃の範囲で、最高温度での保持時間が２〜３時間、雰囲気は大気中での焼成が一般的であるが、本発明では積層セラミックコンデンサに適用する場合に内部電極層として卑金属を用いることができる非還元性の誘電体磁器への可能性を有するという点で水素−窒素雰囲気の焼成にも対応可能である。また、焼成後の熱処理（再酸化処理）の最高温度が９００〜１１００℃、この熱処理での雰囲気も窒素を主成分とする還元雰囲気であることが好ましい。 The firing temperature is in the range of 1200 to 1400 ° C., the retention time at the maximum temperature is 2 to 3 hours, and the atmosphere is generally fired in the air, but in the present invention, it is applied to a multilayer ceramic capacitor In addition, it is possible to deal with firing in a hydrogen-nitrogen atmosphere in that it has a possibility of a non-reducing dielectric ceramic that can use a base metal as an internal electrode layer. The maximum temperature of the heat treatment (reoxidation treatment) after firing is 900 to 1100 ° C., and the atmosphere in this heat treatment is also preferably a reducing atmosphere containing nitrogen as a main component.
なお、上記本発明に係る混合粉末を用いてグリーンシートを形成し、このグリーンシートの主面に内部電極パターンを形成し、この内部電極パターンを形成したグリーンシートを複数積層して積層体を形成し、上記温度条件で焼成することにより、本発明の誘電体磁器を誘電体層として具備する積層セラミックコンデンサを形成できることはいうまでもない。 A green sheet is formed using the mixed powder according to the present invention, an internal electrode pattern is formed on the main surface of the green sheet, and a laminate is formed by laminating a plurality of green sheets formed with the internal electrode pattern. It goes without saying that a multilayer ceramic capacitor comprising the dielectric ceramic of the present invention as a dielectric layer can be formed by firing at the above temperature conditions.
即ち、本発明の積層セラミックコンデンサは誘電体層および内部電極層を交互に積層したコンデンサ本体の端部に外部電極を具備してなるものであり、前記誘電体層が前記請求項１記載の誘電体磁器からなることを特徴とするものである。 That is, the multilayer ceramic capacitor of the present invention comprises an external electrode at the end of a capacitor body in which dielectric layers and internal electrode layers are alternately laminated, and the dielectric layer is the dielectric according to claim 1. It consists of a body porcelain.
また本発明の誘電体磁器の製法は、組成が（Ｂａ１−ｘ−ｙＳｒｘＣａｙ）ｍ（Ｔｉ１−ｚＺｒｚ）Ｏ３と表した時、各構成元素の組成範囲が、０≦ｘ≦０．５、０＜ｙ＜０．１０、０．４≦ｚ≦０．６、０．９９５≦ｍ≦１．０１０の範囲にある誘電体粉末を主成分粉末に、組成式Ｂａ１−ｐＣａｐＴｉＯ３（ｐ＝０．０１〜０．１）で表される副成分粉末およびＭｇ、Ｍｎ、希土類元素のそれぞれの酸化物粉末を添加した混合粉末を調製し、その混合粉末を所定形状に成形し焼成して得られる誘電体磁器の製法であって、前記主成分粉末の平均粒径が０．２μｍ以上０．５μｍ以下であり、また、副成分粉末の平均粒径が０．０２μｍ以上０．１μｍ以下であることを特徴とするものであり、特に、主成分粉末に添加する添加物の成分は、主成分粉末１００質量部に対して、それぞれ、Ｍｇ＝０．０４〜０．１４質量部、希土類元素＝０．１〜１．５質量部、Ｍｎ＝０．０４〜０．３質量部であることが望ましいものである。 The method of the dielectric ceramic of the present invention, when the composition is expressed as (Ba 1-x-y Sr x Ca y) m (Ti 1-z Zr z) O 3, the composition range of each component elements, 0 ≦ x ≦ 0.5, 0 <y <0.10, 0.4 ≦ z ≦ 0.6, 0.995 ≦ m ≦ 1.010 are used as the main component powder, and the composition formula Ba 1-p Ca p TiO 3 subcomponent powder and Mg is expressed by (p = 0.01~0.1), Mn, to prepare a mixed powder prepared by adding each of the oxide powders of rare earth elements, a mixture powder Is formed into a predetermined shape and fired to obtain a dielectric ceramic, wherein the main component powder has an average particle size of 0.2 μm or more and 0.5 μm or less, and the subcomponent powder has an average particle size of It is characterized by being 0.02 μm or more and 0.1 μm or less, and in particular, added to the main component powder The components of Mg are 0.04 to 0.14 parts by mass, rare earth elements are 0.1 to 1.5 parts by mass, and Mn is 0.04 to 0.3 parts with respect to 100 parts by mass of the main component powder. A mass part is desirable.
用いた主成分粉末であるＢＳＣＴＺ粉末の平均粒径および組成、ならびに副成分粉末であるＢＣＴ粉末の平均粒径、組成および添加量、ガラス粉末として加えたＳｉＯ２粉末量、焼成温度および誘電体磁器の特性を表１に示した。ここで、ＢＳＣＴＺ粉末は、ＢＳＣＴＺ粉末１００質量部に対して、Ｍｇ（ＭｇＯ）、Ｙ（Ｙ２Ｏ３）、Ｍｎ（ＭｎＣＯ３）をそれぞれ０．３、０．７、０．２質量部を添加して含有させた
上記粉末を直径５ｍｍのジルコニアボールを用いて、溶媒としてトルエンとアルコールとの混合溶媒を添加し湿式混合した。次に、湿式混合した粉末にポリビニルブチラール樹脂およびトルエン・アルコールの混合溶媒を添加し、同じく直径５ｍｍのジルコニアボールを用いて湿式混合して、直径１６ｍｍ、厚み１ｍｍのタブレット状に成形し、これを水素―窒素混合ガス雰囲気中にて焼成して試料を作製した。
Average particle size and composition of BSCTZ powder used as main component powder, average particle size, composition and addition amount of BCT powder as subcomponent powder, amount of SiO 2 powder added as glass powder, firing temperature and dielectric ceramic The characteristics are shown in Table 1. Here, the BSCTZ powder has 0.3, 0.7, and 0.2 parts by mass of Mg (MgO), Y (Y 2 O 3 ), and Mn (MnCO 3 ), respectively, with respect to 100 parts by mass of the BSCTZ powder. The above powder was added and contained in a zirconia ball having a diameter of 5 mm, and a mixed solvent of toluene and alcohol was added as a solvent and wet mixed. Next, a mixed solvent of polyvinyl butyral resin and toluene / alcohol is added to the wet-mixed powder, and wet-mixed using a zirconia ball having the same diameter of 5 mm to form a tablet with a diameter of 16 mm and a thickness of 1 mm. A sample was prepared by firing in a hydrogen-nitrogen mixed gas atmosphere.
次に、上記誘電体磁器を構成する主結晶粒子の平均粒径は走査型電子顕微鏡（ＳＥＭ）により求めた。研磨面をエッチングし、電子顕微鏡写真内の結晶粒子を任意に２０個選択し、インターセプト法により各結晶粒子の最大径を求め、それらの平均値（Ｄ５０）を求めた。 Next, the average grain size of the main crystal particles constituting the dielectric ceramic was determined by a scanning electron microscope (SEM). The polished surface was etched, 20 crystal particles in the electron micrograph were arbitrarily selected, the maximum diameter of each crystal particle was determined by the intercept method, and the average value (D50) was determined.
次に、上記誘電体磁器を厚さ２００μｍに研磨加工し、試料上下面にスパッタ法によりＡｕ電極を形成した。電気特性はＬＣＲメータを用いて−２５℃〜８５℃の温度範囲で、ＡＣ：１Ｖ、測定周波数：１ｋＨｚの条件で静電容量および誘電損失を測定し比誘電率を算出した。比誘電率の温度係数（×１０−６／℃）は、−４０℃〜８５℃の範囲での各温度での温度変化率である。 Next, the dielectric ceramic was polished to a thickness of 200 μm, and Au electrodes were formed on the upper and lower surfaces of the sample by sputtering. The electrical characteristics were calculated by measuring the capacitance and dielectric loss using an LCR meter in the temperature range of −25 ° C. to 85 ° C. under the conditions of AC: 1 V and measurement frequency: 1 kHz. The temperature coefficient (× 10 −6 / ° C.) of the relative dielectric constant is the rate of temperature change at each temperature in the range of −40 ° C. to 85 ° C.
また、信頼性は高温負荷寿命の評価により行った。その条件は２７５℃の恒温糟中に保持した試料に直流４００Ｖを印加し、抵抗値が初期値に比べ、１桁低下した時間とした。 Reliability was evaluated by evaluating the high temperature load life. The condition was a time in which DC 400 V was applied to a sample held in a constant temperature bath at 275 ° C., and the resistance value decreased by an order of magnitude compared to the initial value.
主結晶粒子中央部および結晶粒子の界面からの距離５ｎｍの位置におけるカルシウムの濃度は透過電子顕微鏡に付設した分析装置により求めた。この場合、結晶粒子の粒界側から中央部側にむけて直線的に走査して検出されたカウントから元素濃度を求めた。また、磁器中のＣａ量はＩＣＰ法を用いて分析した。試料Ｎｏ．２５は、組成を（Ｂａ１−ｘ−ｙＳｒｘＣａｙ）ｍ（Ｔｉ１−ｚＺｒｚ）Ｏ３と表した時のｍが０．９８であり、一方、試料Ｎｏ．２６はｍが１．０２であり、ｍの値が本発明の範囲からはずれるものである。組成は、得られた磁器を硼酸と炭酸ナトリウムと混合し溶融させたものを塩酸に溶解させて、各元素を１０００ｐｐｍ含むの標準液を希釈したものを標準試料としてＩＣＰ発光分光分析にかけて定量化した。結果を表１、２に示した。
表１、２の結果から明らかなように、本発明の組成範囲で規定した誘電体磁器では、いずれも比誘電率が３１５以上、誘電損失が０．８％以下、比誘電率の変化率である温度係数も−１０３０×１０−６／℃以下、高温負荷寿命（ＭＴＴＦ）が６９時間以上であった。 As is clear from the results in Tables 1 and 2, all of the dielectric ceramics defined in the composition range of the present invention have a relative dielectric constant of 315 or more, a dielectric loss of 0.8% or less, and a change rate of the relative dielectric constant. A certain temperature coefficient was −1030 × 10 −6 / ° C. or less, and a high temperature load life (MTTF) was 69 hours or more.
特に、粒径が０．１μｍ以下のＢＣＴ粉末を所定量添加して主結晶粒子の平均粒径を０．２〜０．５μｍとして得られた本発明に係る誘電体磁器では、粒界から５ｎｍの領域での平均カルシウム濃度と、粒子中心部におけるカルシウムの濃度の比は０．７以下であり、それら本発明の試料Ｎｏ．３〜Ｎｏ．１７、Ｎｏ．１９〜２１では、比誘電率が３１５以上、誘電損失が０．８％以下、比誘電率の変化率である温度係数も−９９０×１０−６／℃以下、高温負荷寿命（ＭＴＴＦ）が７１時間以上であった。 In particular, in a dielectric ceramic according to the present invention obtained by adding a predetermined amount of BCT powder having a particle size of 0.1 μm or less and having an average particle size of main crystal particles of 0.2 to 0.5 μm, 5 nm from the grain boundary. The ratio of the average calcium concentration in the region and the concentration of calcium in the center of the particle is 0.7 or less. 3-No. 17, no. 19 to 21, the dielectric constant is 315 or more, the dielectric loss is 0.8% or less, the temperature coefficient that is the rate of change of the dielectric constant is −990 × 10 −6 / ° C. or less, and the high temperature load life (MTTF) is 71. It was over time.
本発明の誘電体磁器のキュリー温度は上記した−４０℃〜８５℃の範囲での比誘電率の温度係数から推定して、いずれも−４０℃〜８５℃の使用温度範囲よりも低温側にシフトしていることがわかった。 The Curie temperature of the dielectric ceramic of the present invention is estimated from the temperature coefficient of the relative dielectric constant in the range of −40 ° C. to 85 ° C., and both are on the lower temperature side than the operating temperature range of −40 ° C. to 85 ° C. I found out that it was shifting.
一方、本発明の範囲外の組成を有する試料では、温度変化率が大きくなり、また、Ｚｒ濃度が大きい試料Ｎｏ．２２では、転移温度が低温化しすぎて比誘電率が１９５であった。常誘電相−強誘電相の相転移温度が−５０℃程度で十分低温化できていないためと考えられた。また、Ｓｒ濃度の高い試料Ｎｏ．２３では、同様に転移温度が低温下して比誘電率が２３０以下であった。組成を（Ｂａ１−ｘ−ｙＳｒｘＣａｙ）ｍ（Ｔｉ１−ｚＺｒｚ）Ｏ３と表した時のｍが０．９８である試料Ｎｏ．２５、および、ｍが１．０２である試料Ｎｏ．２６では、ｍの値が本発明の範囲からはずれているため、比誘電率が低く、誘電損失が大きかった。 On the other hand, in the sample having a composition outside the range of the present invention, the temperature change rate is large, and the sample No. In No. 22, the transition temperature was too low and the relative dielectric constant was 195. This is considered to be because the phase transition temperature between the paraelectric phase and the ferroelectric phase was about −50 ° C. and could not be sufficiently lowered. In addition, the sample No. In No. 23, similarly, the transition temperature was lowered and the relative dielectric constant was 230 or less. When the composition is expressed as (Ba 1-xy Sr x Ca y ) m (Ti 1-z Zr z ) O 3 , m is 0.98. 25 and sample No. with m being 1.02. In No. 26, since the value of m deviated from the range of the present invention, the relative dielectric constant was low and the dielectric loss was large.
Claims (3)
前記Ｂａ、Ｓｒ、Ｃａ、ＴｉおよびＺｒが、
Ｂａ＝０．４５〜１．０１、
Ｓｒ＝０〜０．５、
Ｃａ＝０〜０．０５、
Ｔｉ＝０．４〜０．６、
Ｚｒ＝０．４〜０．６
のモル比であるとともに、
ＴｉおよびＺｒの合量モル数を１としたときに、Ｂａ、ＳｒおよびＣａの合量のモル数ｍが０．９９５〜１．０１の範囲であることを特徴とする誘電体磁器。 A dielectric ceramic formed of main crystal particles each containing Ba, Sr, Ca, Ti and Zr as oxides,
Ba, Sr, Ca, Ti and Zr are
Ba = 0.45 to 1.01,
Sr = 0-0.5,
Ca = 0-0.05,
Ti = 0.4-0.6,
Zr = 0.4-0.6
As well as the molar ratio of
A dielectric ceramic, wherein the total number of moles m of Ba, Sr, and Ca is in the range of 0.995 to 1.01, where the total number of moles of Ti and Zr is 1.
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| JP2006176388A (en) * | 2004-11-26 | 2006-07-06 | Kyocera Corp | Dielectric ceramic and method of manufacturing the same |
| WO2012124736A1 (en) * | 2011-03-16 | 2012-09-20 | 株式会社 村田製作所 | Derivative ceramics and laminated ceramic capacitor |
| JP2013112569A (en) * | 2011-11-29 | 2013-06-10 | Tdk Corp | Dielectric ceramic composition and ceramic electronic component |
| US20150274600A1 (en) * | 2014-03-28 | 2015-10-01 | Tdk Corporation | Dielectric composition and electronic component |
| US20160002114A1 (en) * | 2013-03-26 | 2016-01-07 | Ngk Insulators, Ltd. | Dielectric ceramic composition and composite ceramic structure |
| US20170015590A1 (en) * | 2015-07-16 | 2017-01-19 | National Taipei University Of Technology | Ceramic capacitor dielectric material |
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| JP6686676B2 (en) | 2016-04-28 | 2020-04-22 | 株式会社村田製作所 | Multilayer ceramic capacitor and manufacturing method thereof |
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| US9963393B2 (en) * | 2015-07-16 | 2018-05-08 | National Taipei University Of Technology | Ceramic capacitor dielectric material |
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