JP2004075452A - Dielectric ceramic composition and ceramic capacitor - Google Patents
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【０００１】
【発明の属する技術分野】
この発明は、耐還元性を有し、Ｎｉなどの卑金属を内部電極の材料とする温度補償用磁器コンデンサの誘電体層の材料として好適な誘電体磁器組成物とこの誘電体磁器組成物を誘電体層の材料とした磁器コンデンサに関するものである。
【０００２】
【従来の技術】
磁器コンデンサとして、例えば、積層タイプの磁器コンデンサは次のような方法によって製造されている。すなわち、ドクターブレード法等によりセラミックグリーンシートを作成し、このグリーンシート上に内部電極となる金属粉末のペーストを印刷し、これらを複数枚積み重ねて熱圧着し、大気雰囲気中において１３００℃以上の温度で焼成して焼結体を作り、内部電極と導通する外部電極を焼結体の端面に焼き付けている。
【０００３】
ここで、内部電極の材料としては、パラジウム、白金、銀−パラジウムのような貴金属であれば、上記製造条件下でも酸化しないため、この様な貴金属がこれまで多くの積層磁器コンデンサに使用されていた。
【０００４】
しかし、上記のような貴金属は、内部電極の材料として優れた特性を有しているが、反面、高価であるためコスト高の原因になっていた。そこで、このような問題を解決する手段として、内部電極の材料としてニッケル等の卑金属を用いることが試みられている。
【０００５】
しかし、内部電極の材料として、例えばニッケルを用いると、大気雰囲気中における焼成でニッケルが酸化されるため、内部電極を形成することができなくなる。このような卑金属の酸化を防止するためには、還元雰囲気中で焼成を行なわなければならないが、還元雰囲気中で焼成を行なうとセラミックは還元されて半導体化し、絶縁性が低下してコンデンサとして機能しなくなる。
【０００６】
そこで、還元性雰囲気中で焼成しても半導体化しない、絶縁性の高い誘電体材料が種々開発されている。そして、そのような材料の一つとして耐還元性を有するＣａ−Ｂａ−Ｓｒ−Ｔｉ−Ｚｒ−Ｏ複合ペロブスカイト系磁器組成物が、温度補償用磁器コンデンサの誘電体層の材料として使用されている。
【０００７】
【発明が解決しようとする課題】
しかし、Ｃａ−Ｂａ−Ｓｒ−Ｔｉ−Ｚｒ−Ｏ複合ペロブスカイト系誘電体磁器組成物は、還元性雰囲気中での焼成により粒成長し易く、このため機械的強度が悪化し易いという問題があった。
【０００８】
この発明の目的は、できるだけ機械的強度の高いＣａ−Ｂａ−Ｓｒ−Ｔｉ−Ｚｒ−Ｏ複合ペロブスカイト系誘電体磁器組成物を備えた磁器コンデンサを提供することにある。
【０００９】
具体的には、非酸化性雰囲気中における１２５０℃以下の焼成温度で得られ、誘電体層を構成している誘電体磁器組成物の比誘電率εｓ が５０以上、Ｑが５０００以上、温度係数ＴＣＣが−１０００ｐｐｍ〜−５０ｐｐｍ、抗折強度が１４０００ｋｇｆ／ｍｍ２と、その特性が従来のものより更に優れた誘電体磁器組成物及び磁器コンデンサを提供することにある。
【００１０】
【課題を解決するための手段】
この発明に係る誘電体磁器組成物は、主成分に副成分を添加してなる混合物を焼成して焼結させたものからなり、前記主成分が、（Ｃａ１−ｘＬｘ）ｋ（Ｚｒ１−ｙＴｉｙ）Ｏ３（但し、ＬはＢａ及び又はＳｒ、ｘは０．１〜０．９、ｋは０．９〜１．１、ｙは０．１５〜０．５０）で表わされる物質からなり、前記副成分が、ガラス成分と、Ｍｎ２Ｏ３と、ＭＯ（ＭＯはＣｒＯ３／２，ＮｉＯ，ＣｏＯ３／２及びＶＯ５／２から選択された１種又は２種以上の酸化物）とからなり、該ガラス成分の添加量が主成分に対して０．１〜５ｗｔ％、該Ｍｎ２Ｏ３の添加量がＭｎとして０．１〜３ａｔｍ％、該ＭＯの添加量がＭ（Ｃｒ，Ｎｉ，Ｃｏ及びＶから選択された１種又は２種以上の元素）として０．０５〜２ａｔｍ％であることを特徴とするものである。
【００１１】
また、この発明に係る磁器コンデンサは１又は２以上の卑金属を材料とする誘電体層と、該誘電体層を各々挟持している少なくとも２以上の内部電極とを備え、該誘電体層が主成分に副成分を添加してなる混合物を非酸化性雰囲気中で焼成して焼結させた前記誘電体磁器組成物からなるものである。
【００１２】
ここで、主成分のＡ／Ｂ比であるｋの値を０．９〜１．１としたのは、ｋの値が０．９未満になったり、１．１を越えると焼結性が悪化したり、Ｑが悪化するが、ｋの値が０．９〜１．１の範囲ではこのようなことがないからである。
【００１３】
また、Ｌ（Ｂａ及び／又はＳｒ）の割合であるｘの値を０．１〜０．９としたのは、ｘの値が０．１未満になると温度係数ＴＣＣがマイナス変動し、ｘの値が０．９を越えると誘電率εｓが低下するが、ｘの値が０．１〜０．９の範囲ではこのようなことがないからである。
【００１４】
また、Ｔｉの割合であるｙの値を０．１５〜０．５０としたのは、ｙの値が０．１５未満になると誘電率εｓが低下し、ｙの値が０．５０を越えると温度係数ＴＣＣがマイナス変動するが、ｙの値が０．１５〜０．５０の範囲ではこのようなことがないからである。
【００１５】
また、ガラス成分の割合を主成分に対して０．１〜５ｗｔ％としたのは、ガラス成分の割合が０．１ｗｔ％未満になると焼結性が悪化したり、Ｑが悪化し、ＳｉＯ２の割合が５ｗｔ％を越えると粒成長により機械的強度が低下するが、ガラス成分の割合が０．１〜５ｗｔ％の範囲ではこのようなことがないからである。なお、ガラス成分としては、Ｌｉ−ＳｉＯ２系ガラス、Ｂ−ＳｉＯ２系ガラスまたはＳｉＯ２が使用可能である。
【００１６】
また、Ｍｎ２Ｏ３の割合をＭｎとして０．１〜３ａｔｍ％としたのは、Ｍｎ２Ｏ３の割合がＭｎとして０．１ａｔｍ％未満になると半導体化してＱが低下し、Ｍｎ２Ｏ３の割合がＭｎとして３ａｔｍ％を越えると粒成長により強度が低下するが、Ｍｎ２Ｏ３の割合がＭｎとして０．１〜３ａｔｍ％の範囲ではこのようなことがないからである。
【００１７】
また、ＭＯ（ＭＯはＣｒＯ３／２，ＮｉＯ，ＣｏＯ３／２及びＶＯ５／２から選択された１種又は２種以上の酸化物）の割合をＭ（Ｃｒ，Ｎｉ，Ｃｏ及びＶから選択された１種又は２種以上の元素）として０．０５〜２ａｔｍ％としたのは、ＭＯの割合がＭとして０．０５ａｔｍ％未満になると粒成長により機械的強度が低下し、ＭＯの割合がＭとして２ａｔｍ％を越えると半導体化によりＱが低下するが、ＭＯの割合がＭとして０．０５〜２ａｔｍ％の範囲ではこのようなことがないからである。
【００１８】
【実施例】
純度９９．９％の炭酸カルシウム（ＣａＣＯ３）、炭酸ストロンチウム（ＳｒＣＯ３）、炭酸バリウム（ＢａＣＯ３）、酸化ジルコニウム（ＺｒＯ２）、酸化チタン（ＴｉＯ２）を主成分の出発原料として用意し、これらを混合、焼結した後に得られる誘電体組成物が、表１▲１▼、表１▲２▼に示される条件を満足するように、各々秤量した。
【００１９】
【表１▲１▼】
【表１▲２▼】
ここで、表１▲１▼、表１▲２▼のｘの欄は主成分の組成式（Ｃａ１−ｘＬｘ）ｋ（Ｚｒ１−ｙＴｉｙ）Ｏ３におけるＬと（Ｌ＋Ｃａ）との比（ｘ）を、ｙの欄は主成分の組成式におけるＴｉと（Ｔｉ＋Ｚｒ）との比（ｙ）を、ｋの欄は主成分の組成式における（Ｃａ＋Ｌ）の比（ｋ）を示している。なお、ＬはＢａ及び／又はＳｒを意味している。
【００２２】
次に、これら主成分の出発原料１００重量部とジルコニアボール３００重量部と純水３００重量部をポットミルに入れ、湿式で１５時間撹拌し、得られたスラリーをステンレスバットに移し、これを熱風乾燥機に入れ、１５０℃で４時間乾燥させた。
【００２３】
次に、この乾燥によって得られた固形物を粗粉砕し、得られた粗粉をトンネル炉に入れ、大気雰囲気中において、１２００℃で、２時間仮焼して主成分材料（誘電体のベース材）を得た。
【００２４】
次に、この主成分材料と副成分物質の材料とを混合、焼結した後の誘電体組成物が表１▲１▼、表１▲２▼に示された割合となるように各々の材料の量を秤量し、混合した。
【００２５】
ここで、副成分物質の材料のガラス成分としての酸化珪素（ＳｉＯ２）は純度９９％のものを、酸化マンガン（ＩＩＩ）（Ｍｎ２Ｏ３）、酸化クロム（ＩＩＩ）（Ｃｒ２Ｏ３）はいずれも、純度９９．９％のものを使用した。また、試料Ｎｏ．３以外の、ＮｉＯ，Ｃｏ２Ｏ３，Ｖ２Ｏ５のいずれも純度９９．９％のものを使用した。
【００２６】
次に、この誘電体材料１００重量部に対して、有機バインダーとしてポリブチルフタレートを１５重量部、可塑剤としてジオクチルフタレート（ＤＯＰ）を４０重量部、溶剤としてトルエンを１５０重量部添加し、ボールミルを用いて１５時間、撹拌混合し、スラリーを作成した。
【００２７】
次に、このスラリーを真空脱泡機に入れて脱泡し、このスラリーをリバースロールコーターによってポリエステルフィルム上に薄膜状に塗布し、これを１００℃で乾燥し、厚さ６μｍのセラミック未焼結シート（セラミックグリーンシート）を得た。
【００２８】
一方、平均粒径０．５μｍのＮｉ粉末と、エチルセルロースをブチルカルビトールに溶解させたものとを撹拌機に入れ、充分に混合、混練して内部電極用の導電ペーストを得た。
【００２９】
そして、この導電ペーストを用いて、未焼結シート上に、短冊状の導電パターンをスクリーン印刷した。この時、導電パターンが、長手方向に約１／３ずれるよう、２種類の導電パターンを印刷した。
【００３０】
次に、２種類の導電パターンを印刷した２種類の未焼結シートを交互に５１枚（誘電体５０層）積層し、この積層によって得られた積層物の上下に、導電パターンが印刷されていない未焼結シートを積層した。
【００３１】
そして、この積層体を７０℃の温度の下で５０ＭＰａの圧力を加えて押圧し、これらを圧着した。その後、この積層体を格子状に切断し、積層体チップ（素子）を得た。
【００３２】
次に、この積層体チップを大気雰囲気中において１００℃／時間の速度で６００℃まで昇温させ、積層体チップの内部に含まれている有機バインダを加熱除去させた。そして、炉の雰囲気を大気雰囲気からＨ２（２体積％）＋Ｎ２（９８体積％）の混合雰囲気に切り替え、１００℃／時間の速度で１２５０℃（焼成温度）まで昇温させ、２時間保持した後、１００℃／時間の速度で６００℃まで降温し、雰囲気を大気雰囲気に切り替え、６００℃で３０時間保持して酸化処理を行ない、その後、室温まで冷却した。
【００３３】
このようにして、積層体チップを焼成し、電極が露出した状態で焼結された焼結体チップの側面に、Ｎｉ粉末とガラスフリットとビヒクルからなる導電ペーストを塗布して乾燥し、大気中５５０℃、１５分間焼き付けてＮｉ電極層を形成する。
【００３４】
更に、この上に無電解メッキによりＣｕを被着させ、この上に電解メッキによりＰｂ−Ｓｎ半田層を被着させて、一対の外部電極を形成して積層セラミックコンデンサを得た。
【００３５】
なお、得られた積層セラミックコンデンサは、２ｍｍ（Ｌ）×１．２５ｍｍ（Ｗ）×１ｍｍ（Ｔ）（２１２タイプ）であり、内部電極の交差面積は１ｍｍ２、誘電体層の１層当たりの厚みは４μｍであった。
【００３６】
次に、完成した積層セラミックコンデンサの比誘電率εｓ、品質係数Ｑ、温度係数ＴＣＣ、抗折強度を測定したところ、表２▲１▼，▲２▼に示す通りであった。
【００３７】
なお、電気的特性及び機械的特性は次の要領で測定した。
【００３８】
（Ａ）比誘電率εｓ、品質係数Ｑ
ＬＣＲメータを用い、温度２５℃、周波数１ＭＨｚ、交流電圧１Ｖ（実効値）の条件で、静電容量を測定した。得られた静電容量と内部電極の交差面積と誘電体層１層当たりの厚みから、比誘電率εｓを算出した。
【００３９】
（Ｂ）温度係数ＴＣＣ
２５℃及び１２５℃の場合の静電容量を上記のようにして測定し、この静電容量から温度変化に対する容量変化率を算出した。
【００４０】
（Ｃ）抗折強度
グリーンシートのみを積層した積層体を、上述の積層体チップと同条件で焼成し、試料を作成した。これを用いて３点曲げ試験を行い、抗折強度（ｋｇｆ／ｍｍ２）を求めた。
【００４１】
【表２▲１▼】
【表２▲２▼】
表２▲１▼，▲２▼に示す結果から、試料Ｎｏ．４２に示すようにｋの値が０．８５の場合はＱが４３００と目標値である５０００が得られず、試料Ｎｏ．４５に示すようにｋの値が１．１５の場合はＱが３９００と目標値である５０００が得られず、且つ抗折強度が１３４００ｋｇｆ／ｍｍ２と目標値である１４０００ｋｇｆ／ｍｍ２が得られないが、試料Ｎｏ．４３，４４に示すようにｋの値が０．９〜１．１の場合は所望の特性が得られることがわかる。
【００４４】
また、表２▲１▼，▲２▼に示す結果から、試料Ｎｏ．３４に示すようにｘの値が０の場合は温度係数ＴＣＣが−１１０３ｐｐｍと目標値である−１０００ｐｐｍ〜−５０ｐｐｍを外れ、試料Ｎｏ．３７に示すようにｘの値が１の場合は誘電率εｓが４６と目標値である５０が得られないが、試料Ｎｏ．３５，３６に示すようにｘの値が０．１〜０．９の場合は所望の特性が得られることがわかる。
【００４５】
また、表２▲１▼，▲２▼示す結果から、ＬはＢａ＋Ｓｒの形での添加だけでなく、試料Ｎｏ．３８〜４１に示すように、Ｂａ単独でもよいし、Ｓｒ単独でも良いことがわかる。
【００４６】
また、表２▲１▼，▲２▼に示す結果から、試料Ｎｏ．３０に示すようにｙの値が０．１３の場合は誘電率εｓが４５と目標値である５０が得られず、且つ温度係数ＴＣＣが−４３ｐｐｍと目標値である−１０００ｐｐｍ〜−５０ｐｐｍを外れ、試料Ｎｏ．３３に示すようにｙの値が０．６の場合は温度係数ＴＣＣが−１２３０と目標値である−１０００ｐｐｍ〜−５０ｐｐｍを外れてしまうが、試料Ｎｏ．３１，３２に示すようにｙの値が０．１５〜０．５０の場合は所望の特性が得られることがわかる。
【００４７】
また、表２▲１▼，▲２▼に示す結果から、試料Ｎｏ．２０に示すようにガラス成分としてのＳｉＯ２の割合が０の場合はＱが２３００と目標値である５０００が得られず、試料Ｎｏ．２３に示すようにＳｉＯ２の割合が１０ｗｔ％の場合は抗折強度が１３９００ｋｇｆ／ｍｍ２と目標値である１４０００ｋｇｆ／ｍｍ２が得られないが、試料Ｎｏ．２１，２２に示すようにＳｉＯ２の割合が０．１〜５ｗｔ％の場合は所望の特性が得られることがわかる。なお、試料Ｎｏ．２４〜２９に示すように、ＳｉＯ２の代わりにＬｉ−ＳｉＯ２系ガラス、Ｂ−ＳｉＯ２系を用いても同様の特性が得られる。
【００４８】
また、表２▲１▼，▲２▼に示す結果から、試料Ｎｏ．１６に示すようにＭｎ２Ｏ３の割合がＭｎとして０．０５ａｔｍの場合はＱが４４００と目標値である５０００が得られず、試料Ｎｏ．１９に示すようにＭｎ２Ｏ３の割合がＭｎとして４ａｔｍ％の場合は抗折強度が１３６００ｋｇｆ／ｍｍ２と目標値である１４０００ｋｇｆ／ｍｍ２が得られなくなるが、試料Ｎｏ．１７，１８に示すようにＭｎ２Ｏ３の割合がＭｎとして０．１〜３ａｔｍ％の場合は所望の特性が得られることがわかる。
【００４９】
また、表２▲１▼，▲２▼に示す結果から、試料Ｎｏ．１に示すようにＭＯの割合がＭとして０ａｔｍ％の場合は抗折強度が１２９００ｋｇｆ／ｍｍ２と、目標値である１４０００ｋｇｆ／ｍｍ２が得られず、試料Ｎｏ．５に示すようにＭＯの割合がＭとして４ａｔｍ％の場合はＱが３８００と目標値である５０００が得られないが、ＭＯの割合がＭとして０．０５〜２ａｔｍ％の場合は所望の特性が得られることがわかる。
【００５０】
また、表２▲１▼，▲２▼に示す結果から、試料Ｎｏ．６〜１５に示すように、ＭＯはＣｒＯ３／２に限定されるものではなく、ＣｒＯ３／２，ＮｉＯ，ＣｏＯ３／２及びＶＯ５／２から選択された１種又は２種以上の酸化物であれば同様の結果が得られることがわかる。
【００５１】
また、表２▲１▼，▲２▼に示す結果から、試料Ｎｏ．４６〜５５に示すように、ｘ，ｙ，ｋ，ｔが組成限界値（最大値）になっている場合、ＣｒＯ３／２添加量が最低量であっても抗折強度の向上が認められることがわかる。
【００５２】
【発明の効果】
この発明によれば、比誘電率εｓ が５０以上、Ｑが５０００以上、温度係数ＴＣＣが−１０００ｐｐｍ〜−５０ｐｐｍ、抗折強度が１４０００ｋｇｆ／ｍｍ２以上の特性を備えた耐還元性を有する誘電体磁器組成物及び磁器コンデンサを提供することができる。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention provides a dielectric ceramic composition having reduction resistance and suitable as a material for a dielectric layer of a ceramic capacitor for temperature compensation using a base metal such as Ni as a material of an internal electrode, and a dielectric ceramic composition comprising the same. The present invention relates to a ceramic capacitor used as a material of a body layer.
[0002]
[Prior art]
As a porcelain capacitor, for example, a laminated type porcelain capacitor is manufactured by the following method. That is, a ceramic green sheet is prepared by a doctor blade method or the like, a paste of a metal powder to be used as an internal electrode is printed on the green sheet, a plurality of these are stacked and thermocompression-bonded, and a temperature of 1300 ° C. or more is set in an air atmosphere. To form a sintered body, and external electrodes that are electrically connected to the internal electrodes are baked on the end face of the sintered body.
[0003]
Here, as a material of the internal electrode, if it is a noble metal such as palladium, platinum or silver-palladium, it will not be oxidized even under the above manufacturing conditions, and thus such a noble metal has been used in many laminated ceramic capacitors. Was.
[0004]
However, such a noble metal as described above has excellent characteristics as a material for the internal electrode, but on the other hand, it is expensive and causes high cost. In order to solve such a problem, attempts have been made to use a base metal such as nickel as the material of the internal electrode.
[0005]
However, if, for example, nickel is used as the material of the internal electrode, the nickel is oxidized by firing in the air atmosphere, so that the internal electrode cannot be formed. In order to prevent such oxidation of the base metal, firing must be performed in a reducing atmosphere. However, when firing is performed in a reducing atmosphere, the ceramic is reduced to a semiconductor and the insulating properties are reduced, and the ceramic functions as a capacitor. No longer.
[0006]
Therefore, various dielectric materials having high insulating properties, which do not become semiconductor even when fired in a reducing atmosphere, have been developed. As one of such materials, a Ca—Ba—Sr—Ti—Zr—O composite perovskite ceramic composition having reduction resistance has been used as a material for a dielectric layer of a ceramic capacitor for temperature compensation. .
[0007]
[Problems to be solved by the invention]
However, the Ca-Ba-Sr-Ti-Zr-O composite perovskite-based dielectric porcelain composition has a problem that grains are easily grown by firing in a reducing atmosphere, and thus mechanical strength is liable to be deteriorated. .
[0008]
An object of the present invention is to provide a ceramic capacitor including a Ca—Ba—Sr—Ti—Zr—O composite perovskite-based dielectric ceramic composition having as high a mechanical strength as possible.
[0009]
Specifically, the dielectric ceramic composition obtained at a firing temperature of 1250 ° C. or lower in a non-oxidizing atmosphere has a relative dielectric constant εs of 50 or higher, Q of 5000 or higher, and a temperature coefficient of An object of the present invention is to provide a dielectric ceramic composition and a ceramic capacitor having a TCC of -1000 ppm to -50 ppm and a transverse rupture strength of 14000 kgf / mm 2 , which are more excellent in characteristics than conventional ones.
[0010]
[Means for Solving the Problems]
The dielectric ceramic composition according to this invention comprises by firing a mixture obtained by adding the auxiliary component as a main component that is sintered, the main component, (Ca 1-x L x ) k (Zr 1-y Ti y ) O 3 (where L is Ba and / or Sr, x is 0.1 to 0.9, k is 0.9 to 1.1, and y is 0.15 to 0.50) Wherein the auxiliary component is a glass component, Mn 2 O 3 , and MO (MO is one or more selected from CrO 3/2 , NiO, CoO 3/2 and VO 5/2) The glass component is added in an amount of 0.1 to 5 wt% with respect to the main component, the Mn 2 O 3 is added in an amount of 0.1 to 3 atm% as Mn, and the MO is added. Is 0.05 to 2 atm% as M (one or more elements selected from Cr, Ni, Co and V). It is characterized by the following.
[0011]
Further, a ceramic capacitor according to the present invention includes a dielectric layer made of one or more base metals, and at least two or more internal electrodes sandwiching the dielectric layer, and the dielectric layer mainly includes The dielectric porcelain composition is obtained by sintering and sintering a mixture obtained by adding subcomponents to the components in a non-oxidizing atmosphere.
[0012]
Here, the reason why the value of k, which is the A / B ratio of the main component, is 0.9 to 1.1 is that if the value of k is less than 0.9, or if it exceeds 1.1, the sinterability will be poor. The reason for this is that although the value worsens or Q deteriorates, such a phenomenon does not occur when the value of k is in the range of 0.9 to 1.1.
[0013]
Further, the value of x, which is the ratio of L (Ba and / or Sr), is set to 0.1 to 0.9 because the temperature coefficient TCC fluctuates negatively when the value of x is less than 0.1, When the value exceeds 0.9, the dielectric constant εs decreases, but this does not occur when the value of x is in the range of 0.1 to 0.9.
[0014]
The reason why the value of y, which is the proportion of Ti, is 0.15 to 0.50 is that when the value of y is less than 0.15, the dielectric constant εs decreases, and when the value of y exceeds 0.50, This is because the temperature coefficient TCC fluctuates in the minus direction, but this does not occur when the value of y is in the range of 0.15 to 0.50.
[0015]
Further, the reason why the ratio of the glass component is set to 0.1 to 5 wt% with respect to the main component is that when the ratio of the glass component is less than 0.1 wt%, sinterability deteriorates, Q deteriorates, and SiO 2 is deteriorated. If the ratio exceeds 5 wt%, the mechanical strength decreases due to grain growth, but such a phenomenon does not occur when the ratio of the glass component is in the range of 0.1 to 5 wt%. As the glass component, Li-SiO 2 based glass, B-SiO 2 based glass or SiO 2 can be used.
[0016]
Further, the reason that the ratio of Mn 2 O 3 is 0.1 to 3 atm% as Mn is that when the ratio of Mn 2 O 3 is less than 0.1 atm% as Mn, it turns into a semiconductor and Q is reduced, and Mn 2 O 3 When the ratio of Mn exceeds 3 atm% as Mn, the strength decreases due to grain growth, but when the ratio of Mn 2 O 3 is 0.1 to 3 atm% as Mn, such a phenomenon does not occur.
[0017]
The proportion of MO (MO is one or more oxides selected from CrO 3/2 , NiO, CoO 3/2 and VO 5/2 ) is selected from M (Cr, Ni, Co and V). (At least one element selected from the group consisting of one or more elements) is determined to be 0.05 to 2 atm%, because when the proportion of MO is less than 0.05 atm% as M, the mechanical strength decreases due to grain growth, and the proportion of MO decreases. This is because if M exceeds 2 atm%, Q decreases due to semiconductor conversion, but this does not occur when the MO ratio is in the range of 0.05 to 2 atm% as M.
[0018]
【Example】
99.9% pure calcium carbonate (CaCO 3 ), strontium carbonate (SrCO 3 ), barium carbonate (BaCO 3 ), zirconium oxide (ZrO 2 ), and titanium oxide (TiO 2 ) were prepared as starting materials. The dielectric compositions obtained after mixing and sintering these were weighed so as to satisfy the conditions shown in Tables 1-1 and 1-2.
[0019]
[Table 1 [1]]
[Table 1-2]
Here, Table 1 ▲ 1 ▼, Table 1 ▲ 2 ▼ column of x and L in the main component of the composition formula (Ca 1-x L x) k (Zr 1-y Ti y) O 3 and (L + Ca) , The y column shows the ratio (y) between Ti and (Ti + Zr) in the composition formula of the main component, and the k column shows the ratio (k) of (Ca + L) in the composition formula of the main component. ing. In addition, L means Ba and / or Sr.
[0022]
Next, 100 parts by weight of the starting materials of these main components, 300 parts by weight of zirconia balls and 300 parts by weight of pure water are put into a pot mill, stirred for 15 hours in a wet system, and the obtained slurry is transferred to a stainless steel vat and dried with hot air. It was put on a machine and dried at 150 ° C. for 4 hours.
[0023]
Next, the solid obtained by this drying is coarsely pulverized, and the obtained coarse powder is put into a tunnel furnace, and calcined at 1200 ° C. for 2 hours in an air atmosphere to obtain a main component material (base of dielectric). Material).
[0024]
Next, each material was mixed such that the dielectric composition after mixing and sintering the main component material and the subcomponent material had the ratios shown in Tables 1-1 and 1-2. Were weighed and mixed.
[0025]
Here, silicon oxide (SiO 2 ) having a purity of 99% as a glass component of the material of the subcomponent substance is manganese (III) oxide (Mn 2 O 3 ), chromium (III) oxide (Cr 2 O 3 ). In each case, those having a purity of 99.9% were used. Further, the sample No. 3 except, NiO, both of Co 2 O 3, V 2 O 5 was used in a purity of 99.9%.
[0026]
Next, 15 parts by weight of polybutyl phthalate as an organic binder, 40 parts by weight of dioctyl phthalate (DOP) as a plasticizer, and 150 parts by weight of toluene as a solvent are added to 100 parts by weight of the dielectric material, and a ball mill is used. The mixture was stirred and mixed for 15 hours to prepare a slurry.
[0027]
Next, this slurry was put into a vacuum defoaming machine to defoam, and this slurry was applied on a polyester film by a reverse roll coater in the form of a thin film. A sheet (ceramic green sheet) was obtained.
[0028]
On the other hand, a Ni powder having an average particle size of 0.5 μm and a solution of ethyl cellulose dissolved in butyl carbitol were placed in a stirrer, mixed and kneaded sufficiently to obtain a conductive paste for an internal electrode.
[0029]
Then, a strip-shaped conductive pattern was screen-printed on the unsintered sheet using the conductive paste. At this time, two types of conductive patterns were printed so that the conductive patterns were shifted by about 1/3 in the longitudinal direction.
[0030]
Next, two types of unsintered sheets on which two types of conductive patterns are printed are alternately stacked (50 dielectric layers), and conductive patterns are printed on the upper and lower sides of the laminate obtained by this stacking. No unsintered sheets were laminated.
[0031]
Then, the laminate was pressed at a temperature of 70 ° C. by applying a pressure of 50 MPa, and these were pressed. Thereafter, the laminate was cut into a lattice to obtain a laminate chip (element).
[0032]
Next, the temperature of the laminated chip was raised to 600 ° C. at a rate of 100 ° C./hour in an air atmosphere, and the organic binder contained in the laminated chip was removed by heating. Then, the atmosphere of the furnace was switched from the air atmosphere to a mixed atmosphere of H 2 (2% by volume) + N 2 (98% by volume), the temperature was raised to 1250 ° C. (sintering temperature) at a rate of 100 ° C./hour, and held for 2 hours. After that, the temperature was lowered to 600 ° C. at a rate of 100 ° C./hour, the atmosphere was switched to an air atmosphere, and the oxidation treatment was performed at 600 ° C. for 30 hours, followed by cooling to room temperature.
[0033]
In this way, the laminated chip is fired, and a conductive paste composed of Ni powder, glass frit and vehicle is applied to the side surface of the sintered chip sintered with the electrodes exposed, and dried, Baking is performed at 550 ° C. for 15 minutes to form a Ni electrode layer.
[0034]
Further, Cu was deposited thereon by electroless plating, and a Pb-Sn solder layer was deposited thereon by electrolytic plating to form a pair of external electrodes to obtain a multilayer ceramic capacitor.
[0035]
The obtained multilayer ceramic capacitor was 2 mm (L) × 1.25 mm (W) × 1 mm (T) (212 type), the cross area of the internal electrodes was 1 mm 2 , and the dielectric layer per dielectric layer was 1 mm 2 . The thickness was 4 μm.
[0036]
Next, the relative dielectric constant εs, quality factor Q, temperature coefficient TCC, and bending strength of the completed multilayer ceramic capacitor were measured, and the results were as shown in Tables 2-1 and 2-2.
[0037]
The electrical characteristics and the mechanical characteristics were measured as follows.
[0038]
(A) dielectric constant εs, quality factor Q
The capacitance was measured using an LCR meter under the conditions of a temperature of 25 ° C., a frequency of 1 MHz, and an AC voltage of 1 V (effective value). The relative dielectric constant εs was calculated from the obtained capacitance, the intersection area of the internal electrodes, and the thickness per dielectric layer.
[0039]
(B) Temperature coefficient TCC
The capacitance at 25 ° C. and 125 ° C. was measured as described above, and the capacitance change rate with respect to temperature change was calculated from the capacitance.
[0040]
(C) A laminate in which only the bending strength green sheets were laminated was fired under the same conditions as the above-mentioned laminated chip to prepare a sample. Using this, a three-point bending test was performed to determine the bending strength (kgf / mm 2 ).
[0041]
[Table 2-1]
[Table 2 (2)]
From the results shown in Tables 2 (1) and (2), Sample No. 42, when the value of k is 0.85, Q is 4300 and the target value of 5000 cannot be obtained. As shown by 45, when the value of k is 1.15, Q is 3900 and the target value of 5000 cannot be obtained, and the transverse rupture strength is 13400 kgf / mm 2 and the target value of 14000 kgf / mm 2 is obtained. No, but sample no. As shown in 43 and 44, when the value of k is 0.9 to 1.1, it can be seen that desired characteristics can be obtained.
[0044]
Also, from the results shown in Tables 2 (1) and (2), Sample No. As shown in FIG. 34, when the value of x is 0, the temperature coefficient TCC is −1103 ppm, which is outside the target value of −1000 ppm to −50 ppm. As shown in FIG. 37, when the value of x is 1, the dielectric constant εs is 46 and the target value of 50 cannot be obtained, but the sample No. As shown in 35 and 36, when the value of x is 0.1 to 0.9, desired characteristics can be obtained.
[0045]
In addition, from the results shown in Tables 2 (1) and 2), not only L was added in the form of Ba + Sr, As shown in 38 to 41, Ba alone or Sr alone may be used.
[0046]
Also, from the results shown in Tables 2 (1) and (2), Sample No. As shown in FIG. 30, when the value of y is 0.13, the dielectric constant .epsilon.s is 45 and the target value of 50 cannot be obtained, and the temperature coefficient TCC is -43 ppm and deviates from the target value of -1000 ppm to -50 ppm. , Sample No. 33, when the value of y is 0.6, the temperature coefficient TCC is -1230, which is out of the target value of -1000 ppm to -50 ppm. As shown in FIGS. 31 and 32, when the value of y is 0.15 to 0.50, desired characteristics can be obtained.
[0047]
Also, from the results shown in Tables 2 (1) and (2), Sample No. As shown in FIG. 20, when the ratio of SiO 2 as the glass component was 0, Q was 2300, which was the target value of 5000, and the sample No. 20 was not obtained. As shown in FIG. 23, when the ratio of SiO 2 was 10 wt%, the transverse rupture strength was 13900 kgf / mm 2 and the target value of 14000 kgf / mm 2 could not be obtained. As shown in FIGS. 21 and 22, it can be seen that desired characteristics can be obtained when the ratio of SiO 2 is 0.1 to 5 wt%. The sample No. As shown in 24~29, Li-SiO 2 based glass in place of SiO 2, the same characteristics using B-SiO 2 system is obtained.
[0048]
Also, from the results shown in Tables 2 (1) and (2), Sample No. As shown in FIG. 16, when the ratio of Mn 2 O 3 was 0.05 atm as Mn, Q was 4400 and the target value of 5000 could not be obtained. As shown in FIG. 19, when the ratio of Mn 2 O 3 is 4 atm% as Mn, the transverse rupture strength of 13600 kgf / mm 2 and the target value of 14000 kgf / mm 2 cannot be obtained. As shown in FIGS. 17 and 18, when the ratio of Mn 2 O 3 is 0.1 to 3 atm% as Mn, desired characteristics can be obtained.
[0049]
Also, from the results shown in Tables 2 (1) and (2), Sample No. As shown in FIG. 1, when the proportion of MO was 0 atm% as M, the transverse rupture strength was 12900 kgf / mm 2 and the target value of 14000 kgf / mm 2 was not obtained. As shown in FIG. 5, when the ratio of MO is 4 atm% as M, Q is 3800 and the target value of 5000 cannot be obtained, but when the ratio of MO is 0.05 to 2 atm%, the desired characteristics are not obtained. It can be seen that it can be obtained.
[0050]
Also, from the results shown in Tables 2 (1) and (2), Sample No. As shown in 6 to 15, MO is not limited to CrO 3/2, CrO 3/2, NiO, 1 or selected from CoO 3/2 and VO 5/2 or more oxide It can be seen that a similar result can be obtained if the object is a material.
[0051]
Also, from the results shown in Tables 2 (1) and (2), Sample No. As shown in 46 to 55, when x, y, k, and t are composition limit values (maximum values), improvement in transverse rupture strength is observed even when the amount of CrO 3/2 added is the minimum. You can see that.
[0052]
【The invention's effect】
According to the present invention, a reduction-resistant dielectric having characteristics of a relative dielectric constant εs of 50 or more, a Q of 5000 or more, a temperature coefficient TCC of -1000 ppm to -50 ppm, and a flexural strength of 14000 kgf / mm 2 or more. A porcelain composition and a porcelain capacitor can be provided.
Claims (4)
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007055835A (en) * | 2005-08-23 | 2007-03-08 | Tdk Corp | Dielectric ceramic composition and electronic component |
| US7923395B2 (en) * | 2005-04-07 | 2011-04-12 | Kemet Electronics Corporation | C0G multi-layered ceramic capacitor |
| KR101339396B1 (en) | 2012-03-19 | 2013-12-09 | 삼화콘덴서공업주식회사 | Non-reducible low temperature sinterable dielectric ceramic composition for multi layer ceramic capacitor and manufacturing method thereof |
| WO2014156410A1 (en) * | 2013-03-26 | 2014-10-02 | 日本碍子株式会社 | Dielectric porcelain composition and composite ceramic structural body |
| JP2017014094A (en) * | 2015-07-06 | 2017-01-19 | サムソン エレクトロ−メカニックス カンパニーリミテッド． | Dielectric ceramic composition and multilayer ceramic capacitor containing the same |
| KR20200034977A (en) * | 2018-08-06 | 2020-04-01 | 삼성전기주식회사 | Dielectric composition and electronic component using the same |
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2002
- 2002-08-16 JP JP2002237326A patent/JP2004075452A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7923395B2 (en) * | 2005-04-07 | 2011-04-12 | Kemet Electronics Corporation | C0G multi-layered ceramic capacitor |
| JP2007055835A (en) * | 2005-08-23 | 2007-03-08 | Tdk Corp | Dielectric ceramic composition and electronic component |
| KR101339396B1 (en) | 2012-03-19 | 2013-12-09 | 삼화콘덴서공업주식회사 | Non-reducible low temperature sinterable dielectric ceramic composition for multi layer ceramic capacitor and manufacturing method thereof |
| WO2014156410A1 (en) * | 2013-03-26 | 2014-10-02 | 日本碍子株式会社 | Dielectric porcelain composition and composite ceramic structural body |
| US9505661B2 (en) | 2013-03-26 | 2016-11-29 | Ngk Insulators, Ltd. | Dielectric ceramic composition and composite ceramic structure |
| JP2017014094A (en) * | 2015-07-06 | 2017-01-19 | サムソン エレクトロ−メカニックス カンパニーリミテッド． | Dielectric ceramic composition and multilayer ceramic capacitor containing the same |
| KR20200034977A (en) * | 2018-08-06 | 2020-04-01 | 삼성전기주식회사 | Dielectric composition and electronic component using the same |
| KR102409109B1 (en) * | 2018-08-06 | 2022-06-15 | 삼성전기주식회사 | Dielectric composition and electronic component using the same |
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