JP3793549B2 - Dielectric porcelain composition and laminate - Google Patents
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Description
【０００１】
【発明の属する技術分野】
本発明は、高周波領域で使用する電子回路基板や電子部品等に適用される、低温焼成可能な誘電体磁器組成物および、例えば、共振器、コンデンサ、フィルタ等の電子部品、またはこれらを内蔵した基板等の導体を有する積層体に関するものである。
【０００２】
【従来の技術】
従来、誘電体材料として各種誘電体セラミックスが、共振器、コンデンサ、フィルタ等の電子部品やこれらを内蔵した基板に使用されている。そして、近年においては、携帯電話をはじめとする移動体通信等の発達および普及に伴い、電子回路基板や電子部品の材料として、誘電体セラミックスの需要が増大しつつある。
【０００３】
電子回路基板や電子部品において、誘電体セラミックスと内部導体を同時焼成するに際しては、従来の誘電体セラミックスの焼成温度が１１００℃以上という高温であったため、導体材料としては、比較的高融点であるＰｔ、Ｐｄ、Ｗ、Ｍｏ等が使用されていた。これら高融点の導体材料は導通抵抗が大きいため、従来の電子回路基板や電子部品において、共振回路やインダクタンスのＱ値が小さくなってしまい、導体線路の伝送損失が大きくなる等の問題があった。
【０００４】
そこで、係る問題点を解決すべく、導通抵抗の小さいＡｇ、Ｃｕ等と同時焼成可能な、低温焼成の誘電体セラミックスが提案されている。例えば、本出願人が先に出願した特開平８−２０８３３０号公報に開示された誘電体磁器組成物は、ＭｇＯ、ＣａＯ、ＴｉＯ2 とＢ2 Ｏ3 、Ｌｉ2 ＣＯ3 からなるものであり、９００〜１０５０℃の比較的低温でＡｇやＣｕ等の内部導体と同時に焼成でき、誘電体磁器の比誘電率εｒが１８以上、測定周波数７ＧＨｚでのＱ値が２０００以上、かつ共振周波数の温度係数τｆが±４０以内の優れた特性を有し、高周波電子部品の小型化と高性能化を実現できるものであった。
【０００５】
【発明が解決しようとする課題】
しかしながら、特開平８−２０８３３０号公報に開示された誘電体磁器組成物は、焼結における収縮開始温度が８４５〜９６０℃という高温であるため、導体材料との収縮挙動のマッチングが悪く、焼成された基板が反る、歪む等の問題があった。
【０００６】
即ち、導体としては、Ａｇおよび／またはＣｕを主成分とするもの、例えば、Ａｇ、Ｃｕ、あるいはＡｇ、Ｃｕに対してガラス成分やセラミック成分、Ｐｔ、Ｐｄ等の金属を添加したものがあるが、これらの導体は、焼成時における収縮開始温度が高くとも６５０℃程度であるため、上記誘電体磁器組成物の収縮開始温度との差が大きく、これにより、基板が変形する等の問題があった。
【０００７】
本発明は上記課題に鑑みなされたもので、誘電体磁器組成物の収縮開始温度を低くして、導体の収縮開始温度に近づけることができ、ＡｇやＣｕを主成分とする導体と同時焼成した場合でも反りや歪みのない磁器を得ることができる誘電体磁器組成物および積層体を提供することを目的とする。
【０００８】
【課題を解決するための手段】
本発明の誘電体磁器組成物は、金属元素としてＭｇ、ＣａおよびＴｉを含有する複合酸化物であって、これらの金属元素酸化物の重量比による組成式を、ａＭｇＯ・ｂＣａＯ・ｃＴｉＯ２と表した時、ａ、ｂ、ｃが２５．０≦ａ≦３５．０、０．３≦ｂ≦７．０、６０．０≦ｃ≦７０．０、ａ＋ｂ＋ｃ＝１００を満足する主成分と、該主成分１００重量部に対して、Ｂ含有化合物をＢ２Ｏ３換算で３〜２０重量部、アルカリ金属含有化合物をアルカリ金属炭酸塩換算で１〜１０重量部、Ｃｕ含有化合物およびＳｍ含有化合物のうち少なくとも１種をそれぞれＣｕＯ、Ｓｍ２Ｏ３換算で合計０．５〜５重量部含有してなるものである。
【０００９】
また、金属元素としてＭｇ、ＣａおよびＴｉを含有する複合酸化物であって、その組成式が（１００−ｘ）ＭｇＴｉＯ３・ｘＣａＴｉＯ３（但し、式中ｘは重量比を表し、１≦ｘ≦１５）で表される主成分と、該主成分１００重量部に対して、Ｂ含有化合物をＢ２Ｏ３換算で３〜２０重量部、アルカリ金属含有化合物をアルカリ金属炭酸塩換算で１〜１０重量部、Ｃｕ含有化合物およびＳｍ含有化合物のうち少なくとも１種をそれぞれＣｕＯ、Ｓｍ２Ｏ３換算で合計０．５〜５重量部含有してなるものである。
【００１０】
本発明の積層体は、誘電体層を複数積層してなる誘電基体の内部および／または表面に、Ａｇおよび／またはＣｕを主成分とする導体を有する積層体であって、前記誘電体層が、上記誘電体磁器組成物からなるものである。
【００１１】
【作用】
本発明の誘電体磁器組成物では、９００〜１０５０℃の比較的低温で焼成できるとともに、比誘電率εｒやＱ値が高く、かつ共振周波数の温度係数τｆを比較的小さくでき、積層体（高周波電子回路基板や電子部品）の小型化と高性能化を実現できる。
【００１２】
そして、本発明の誘電体磁器組成物では、Ｃｕ含有化合物およびＳｍ含有化合物のうち少なくとも１種をそれぞれＣｕＯ、Ｓｍ２Ｏ３換算で合計０．５〜５重量部含有せしめたので、焼結過程における収縮開始温度を８２０℃以下に低下させることができ、導体の収縮開始温度に近づけることができ、基板や電子部品において、Ａｇ、Ｃｕを主成分とする導体と同時焼成した場合でも基板等の反り、歪み等の発生を抑制することができる。
【００１３】
【発明の実施の形態】
本発明の誘電体磁器組成物は、金属元素としてＭｇ、ＣａおよびＴｉを含有する複合酸化物であって、これらの金属元素酸化物の重量比による組成式を、ａＭｇＯ・ｂＣａＯ・ｃＴｉＯ２と表した時、ａ、ｂ、ｃが２５．０≦ａ≦３５．０、０．３≦ｂ≦７．０、６０．０≦ｃ≦７０．０、ａ＋ｂ＋ｃ＝１００で表される主成分１００重量部に対して、Ｂ含有化合物をＢ２Ｏ３換算で３〜２０重量部、アルカリ金属含有化合物をアルカリ金属炭酸塩換算で１〜１０重量部、Ｃｕ含有化合物およびＳｍ含有化合物のうち少なくとも１種をそれぞれＣｕＯ、Ｓｍ２Ｏ３換算で合計０．５〜５重量部含有してなるものである
【００１４】
本発明において、組成式におけるＭｇＯの重量比ａを２５≦ａ≦３５、ＣａＯの重量比ｂを、０．３≦ｂ≦７としたのは、ＭｇＯの重量比ａが２５重量％未満の場合やＣａＯの重量比ｂが７重量％を超える場合には、共振周波数の温度係数τｆが正に大きくなりすぎてしまうからである。逆に、ＭｇＯの重量比ａが３５重量％を超える場合やＣａＯの重量比ｂが０．３重量％未満の場合には、共振周波数の温度係数τｆが負に大きくなりすぎてしまうからである。よって、ＭｇＯの重量比ａとＣａＯの重量比ｂは、２５．０≦ａ≦３５．０、０．３≦ｂ≦７．０に特定され、とりわけ誘電体磁器の共振周波数の温度係数τｆの観点からは２８．０≦ａ≦３４．０、０．４≦ｂ≦６．５が好ましい。
【００１５】
さらに、ＴｉＯ2 の重量比ｃを６０≦ｃ≦７０としたのは、ＴｉＯ2 の重量比ｃが６０重量％未満あるいは７０重量％を超える場合にはＱ値が低下するからである。よって、ＴｉＯ2 の重量比ｃは６０≦ｃ≦７０に特定され、とりわけ誘電体磁器のＱ値の観点から６４≦ｃ≦６８が好ましい。
【００１６】
また、出発原料をＭｇＴｉＯ３とＣａＴｉＯ３にすることにより、さらにＱ値を向上させ、温度係数の制御が容易となる。つまり、（１００−ｘ）ＭｇＴｉＯ３・ｘＣａＴｉＯ３（但し、式中ｘは重量比を表し、１≦ｘ≦１５）で表される主成分１００重量部に対して、Ｂ含有化合物をＢ２Ｏ３換算で３〜２０重量部、アルカリ金属含有化合物をアルカリ金属炭酸塩換算で１〜１０重量部、Ｃｕ含有化合物およびＳｍ含有化合物のうち少なくとも１種をそれぞれＣｕＯ、Ｓｍ２Ｏ３換算で合計０. ５〜５重量部含有した場合である。
【００１７】
ここで、主成分中のＣａＴｉＯ3 の重量比を１≦ｘ≦１５としたのは、ＣａＴｉＯ3 の重量比が１重量％未満の場合には、共振周波数の温度係数τｆがマイナス側に大きくずれ、また、前記重量比が１５重量％を越える場合には共振周波数の温度係数τｆがプラス側に大きくずれるからである。よって、ＣａＴｉＯ3 の重量比ｘは１〜１５重量％に特定され、とりわけ、誘電体磁器の共振周波数の温度係数τｆの観点からは１〜１０重量％が好ましい。
【００１８】
また、本発明では、上記主成分に対して、Ｂ含有化合物をＢ２Ｏ３換算で３〜２０重量部、アルカリ金属含有化合物をアルカリ金属炭酸塩換算で１〜１０重量部、Ｃｕ含有化合物およびＳｍ含有化合物のうち少なくとも１種をそれぞれＣｕＯ、Ｓｍ２Ｏ３換算で合計０．５〜５重量部含有するものである。
【００１９】
このように主成分１００重量部に対して、Ｂ含有化合物をＢ2 Ｏ3 換算で３〜２０重量部添加したのは、Ｂ2 Ｏ3 の添加量が３重量部未満の場合には１１００℃でも焼結せず、ＡｇまたはＣｕとの同時焼成ができなくなり、逆に２０重量部を超える場合には結晶相が変化し、Ｑ値が低下するからである。よってＢ含有化合物の添加量は、主成分に対してＢ2 Ｏ3 換算で３〜２０重量部に特定され、とりわけ誘電体磁器のＱ値の観点からは３〜９重量部が望ましい。Ｂ含有化合物としては、金属硼素、Ｂ2 Ｏ3 、コレマナイト、ＣａＢ2 Ｏ4 等がある。
【００２０】
また、アルカリ金属含有化合物をアルカリ金属炭酸塩換算で１〜１０重量部添加したのは、アルカリ金属含有化合物、例えばＬｉ含有化合物の添加量が１重量部未満の場合には１１００℃でも焼結せず、ＡｇまたはＣｕとの同時焼成ができなくなり、逆に、１０重量部を超える場合には結晶相が変化し、Ｑ値が低下するからである。よって、アルカリ金属含有化合物の添加量は、主成分１００重量部に対してアルカリ金属炭酸塩換算、例えばＬｉ2 ＣＯ3 換算で１〜１０重量部に特定され、特に誘電体磁器のＱ値の観点からは３〜７重量部が望ましい。
【００２１】
アルカリ金属としては、Ｌｉ、Ｎａ、Ｋを例示することができ、この中でもＬｉが特に望ましい。アルカリ金属含有化合物としては、上記アルカリ金属の炭酸塩、酸化物等を例示することができる。
【００２２】
本発明の誘電体磁器組成物では、主成分１００重量部に対して、Ｃｕ含有化合物およびＳｍ含有化合物のうち少なくとも１種をそれぞれＣｕＯ、Ｓｍ２Ｏ３換算で合計０．５〜５重量部含有するものである。これらが、０．５重量部未満の場合には、誘電体磁器の焼結過程における収縮開始温度が８２０℃よりも高く、添加の効果が得られないからである。一方、該添加物が５重量部を超えると、誘電体磁器の比誘電率εｒあるいはＱ値が低下するからである。誘電体磁器の比誘電率εｒあるいはＱ値の観点からは、合計１〜４重量部が望ましい。
【００２３】
尚、本発明においては、誘電特性に悪影響を及ぼさない範囲でＳｉ、Ｚｎ、Ｍｎ、Ｚｒ等の酸化物を添加含有しても良く、この場合さらに低温焼成が可能となる。
【００２４】
本発明の誘電体磁器組成物は、ボール成分や、不可避不純物として、Ａｌ、Ｆｅ、Ｈｆ、Ｓｎが混入する場合がある。また、結晶相としては、ＭｇＴｉＯ3 、ＣａＴｉＯ3 を主結晶相とし、（Ｍｇ，Ｔｉ）2 （ＢＯ3 ）Ｏが析出する場合がある。また、本発明の誘電体磁器組成物では、その平均結晶粒径は２〜３μｍである。
【００２５】
本発明の誘電体磁器組成物は、例えば、ＭｇＣＯ３、ＣａＣＯ３、ＴｉＯ２の各原料粉末を所定量となるように秤量し、混合粉砕し、これを１１００〜１３００℃の温度で大気中で１〜３時間仮焼する。得られた仮焼物に、例えばＢ２Ｏ３とＬｉ２ＣＯ３の各粉末、およびＣｕＯ、Ｓｍ２Ｏ３のうち少なくとも１種の粉末を所定量となるように秤量し、混合粉砕し、プレス成形やドクターブレード法等の周知の方法により所定形状に成形した後、大気中等の酸化性雰囲気または窒素雰囲気中等の非酸化性雰囲気において、９００〜１０５０℃において０．５〜２．０時間焼成することにより得られる。
【００２６】
また、本発明の積層体は、誘電体層を複数積層してなる誘電基体の内部および／または表面に、Ａｇおよび／またはＣｕを主成分とする導体を有するものであり、誘電体層として、上記した誘電体磁器組成物を用いたものである。
【００２７】
導体としては、Ａｇおよび／またはＣｕを主成分とするもの、例えば、Ａｇ、Ｃｕ、あるいはＡｇ、Ｃｕに対してガラス成分やセラミック成分、Ｐｔ、Ｐｄ等の金属を添加したものも含まれる。これらの金属に対してガラス成分やセラミック成分を添加した導体は内部導体として、また、ＰｔやＰｄを添加した導体は表面導体として好適に用いられる。このような導体は、焼成時における収縮開始温度は高くとも６５０℃程度である。
【００２８】
本発明の誘電体磁器組成物は、Ｃｕ含有化合物およびＳｍ含有化合物のうち少なくとも１種をそれぞれＣｕＯ、Ｓｍ２Ｏ３換算で合計０．５〜５重量部含有することにより、収縮開始温度を８２０℃以下にすることができるため、導体の収縮開始温度に近づけることができる。
【００２９】
【実施例】
実施例１
先ず、純度９９％以上のＭｇＣＯ3 、ＣａＣＯ3 、ＴｉＯ2 の各原料粉末を表１、２に示す量となるように秤量し、該原料粉末に媒体として純水を加えて２４時間、ＺｒＯ2 ボールを用いたボールミルにて混合した後、該混合物を乾燥し、次いで該乾燥物を大気中において１２００℃の温度で１時間仮焼した。
【００３０】
得られた仮焼物にＢ2 Ｏ3 、Ｌｉ2 ＣＯ3 、Ｎｂ2 Ｏ5 、ＣｕＯ、Ｓｍ2 Ｏ3 の粉末を表１、２に示す割合となるように秤量し、上記ボールミルにて２４時間、混合した後、バインダーとしてポリビニルアルコールを１重量％加えてから造粒し、該造粒物を約１ｔ／ｃｍ2 の加圧力でプレス成形して直径約１２ｍｍ、高さ１０ｍｍの円柱状の成形体を成形した。
【００３１】
その後、前記成形体を大気中、４００℃の温度で４時間加熱して脱バインダー処理し、引き続き大気中において表１、２に示す各温度で６０分間焼成した。かくして得られた円柱体の両端面を平面研磨し、誘電体特性評価用試料を作製した。
【００３２】
誘電体特性の評価は、前記評価用試料を用いて誘電体円柱共振器法により、共振周波数を６〜８ＧＨｚに設定して各試料の比誘電率εｒと７ＧＨｚにおける１／ｔａｎδ、即ちＱ値を測定するとともに、−４０〜＋８５℃の温度範囲における共振周波数の温度係数τｆを測定した。これらの結果を表１、２に記載した。尚、表１、２における試料Ｎｏ．２５〜２９は参考試料を示す。
【００３３】
【表１】
【表２】
表１、２によれば、本発明の誘電体磁器組成物では、焼結過程における収縮の開始温度が８００〜８２０℃、焼成温度が９００〜１０５０℃と比較的低温であり、さらに、比誘電率εｒが１８以上、７ＧＨｚにおけるＱ値が２０００以上、かつ共振周波数の温度係数τｆが±４０ｐｐｍ／℃以内の優れた特性を有することができることがわかる。
【００３６】
尚、試料Ｎo.１３、１４はＬｉ2 ＣＯ3 の代わりにＮａ2 ＣＯ3 を用いた。
【００３７】
実施例２
先ず、純度９９％以上のＭｇＴｉＯ3 、ＣａＴｉＯ3 の各原料粉末を表３、４に示す量となるように秤量し、該原料粉末に媒体として純水を加えて２４時間、ＺｒＯ2 ボールを用いたボールミルにて混合した後、該混合物を乾燥し、次いで該乾燥物を大気中１２００℃の温度で１時間仮焼した。
【００３８】
得られた仮焼物にＢ2 Ｏ3 、Ｌｉ2 ＣＯ3 、Ｎｂ2 Ｏ5 、ＣｕＯ、Ｓｍ2 Ｏ3 の粉末を表３、４に示す割合となるように秤量し、上記ボールミルにて２４時間、混合した後、バインダーとしてポリビニルアルコールを１重量％加えてから造粒し、該造粒物を約１ｔ／ｃｍ2 の加圧力でプレス成形して直径約１２ｍｍ、高さ１０ｍｍの円柱状の成形体を作製した。
【００３９】
その後、前記成形体を大気中、４００℃の温度で４時間加熱して脱バインダー処理し、引き続き表３、４に示す各温度で大気中６０分間焼成した。かくして得られた円柱体の両端面を平面研磨し、誘電体特性評価用試料を作製した。誘電体特性の評価は、上記と同様にして求め、その結果を表３、４に記載した。尚、表３、４における試料Ｎｏ．２１〜２５は参考試料を示す。
【００４０】
【表３】
【表４】
表３、４によれば、本発明の誘電体磁器組成物では、焼結過程における収縮の開始温度が８００〜８２０℃、焼成温度が１０５０℃以下と比較的低温であり、さらに、比誘電率εｒが１８以上、Ｑ値が３０００以上、かつ共振周波数の温度係数τｆが±３０ｐｐｍ／℃以内の優れた特性を有することがわかる。
【００４３】
【発明の効果】
本発明の誘電体磁器組成物では、焼結過程における収縮の開始温度を８２０℃以下と導体の収縮開始温度に近づけることができ、また焼成温度も１０５０℃以下と比較的低温であるため、ＡｇやＣｕ等と同時に焼成でき、かつ同時焼成したとしても反りや歪みのない積層体（基板や電子部品）を得ることができる。
【００４４】
さらに、高周波領域において高い比誘電率（１８以上）を有するとともに、Ｑ値（２０００以上）も高く、かつ共振周波数の温度特性（±４０以内）にも優れているため、高周波電子回路基板や電子部品のより一層の小型化と高性能化を実現できる。[0001]
BACKGROUND OF THE INVENTION
The present invention is a dielectric ceramic composition that can be fired at a low temperature and is applied to an electronic circuit board or electronic component used in a high frequency region, and an electronic component such as a resonator, a capacitor, or a filter, or the like. The present invention relates to a laminate having a conductor such as a substrate.
[0002]
[Prior art]
Conventionally, various dielectric ceramics have been used as dielectric materials for electronic parts such as resonators, capacitors, filters, etc., and substrates incorporating them. In recent years, with the development and spread of mobile communications such as mobile phones, the demand for dielectric ceramics as materials for electronic circuit boards and electronic components is increasing.
[0003]
In the simultaneous firing of dielectric ceramics and internal conductors in electronic circuit boards and electronic parts, the firing temperature of conventional dielectric ceramics is as high as 1100 ° C. or higher, so the conductor material has a relatively high melting point. Pt, Pd, W, Mo, etc. were used. Since these high melting point conductor materials have high conduction resistance, there have been problems such as a decrease in the Q value of the resonance circuit and inductance in a conventional electronic circuit board and electronic component, and an increase in transmission loss of the conductor line. .
[0004]
Thus, in order to solve such problems, low-temperature fired dielectric ceramics that can be fired simultaneously with Ag, Cu, etc. having a low conduction resistance have been proposed. For example, the dielectric ceramic composition disclosed in Japanese Patent Application Laid-Open No. 8-208330 filed earlier by the present applicant is composed of MgO, CaO, TiO 2 and B 2 O 3 , Li 2 CO 3 . It can be fired simultaneously with an inner conductor such as Ag or Cu at a relatively low temperature of 900 to 1050 ° C., the dielectric constant εr of the dielectric ceramic is 18 or more, the Q value at a measurement frequency of 7 GHz is 2000 or more, and the temperature coefficient of the resonance frequency It has excellent characteristics with τf within ± 40, and can realize miniaturization and high performance of high-frequency electronic components.
[0005]
[Problems to be solved by the invention]
However, since the dielectric ceramic composition disclosed in Japanese Patent Laid-Open No. 8-208330 has a high shrinkage start temperature in sintering of 845 to 960 ° C., the matching of the shrinkage behavior with the conductor material is poor, and it is fired. There were problems such as warping and distortion of the substrate.
[0006]
That is, as a conductor, there is a conductor mainly composed of Ag and / or Cu, for example, a conductor obtained by adding a metal such as a glass component, a ceramic component, Pt, or Pd to Ag, Cu, or Ag, Cu. Since these conductors have a shrinkage start temperature of about 650 ° C. at the highest, the difference from the shrinkage start temperature of the dielectric ceramic composition is large, thereby causing problems such as deformation of the substrate. It was.
[0007]
The present invention has been made in view of the above problems, and can reduce the shrinkage start temperature of the dielectric ceramic composition to approach the shrinkage start temperature of the conductor, and is simultaneously fired with a conductor mainly composed of Ag or Cu. It is an object of the present invention to provide a dielectric porcelain composition and a laminate capable of obtaining a porcelain free from warpage or distortion.
[0008]
[Means for Solving the Problems]
The dielectric ceramic composition of the present invention is a composite oxide containing Mg, Ca, and Ti as metal elements, and the composition formula based on the weight ratio of these metal element oxides is represented as aMgO · bCaO · cTiO 2. And a main component satisfying a, b, c satisfying 25.0 ≦ a ≦ 35.0, 0.3 ≦ b ≦ 7.0, 60.0 ≦ c ≦ 70.0, a + b + c = 100, 3 to 20 parts by weight of B-containing compound in terms of B 2 O 3 , 1 to 10 parts by weight in terms of alkali metal carbonate, Cu-containing compound and Sm-containing compound with respect to 100 parts by weight of the main component Among them, at least one kind is contained in a total amount of 0.5 to 5 parts by weight in terms of CuO 2 and Sm 2 O 3 .
[0009]
Further, Mg as the metal element, a composite oxide containing Ca and Ti, its composition formula (100-x) MgTiO 3 · xCaTiO 3 ( however, where x represents the weight ratio, 1 ≦ x ≦ 15) The B-containing compound is 3 to 20 parts by weight in terms of B 2 O 3 and the alkali metal-containing compound is 1 to 10 in terms of alkali metal carbonate with respect to 100 parts by weight of the main component represented by 15) A total of 0.5 to 5 parts by weight in terms of CuO 3 and Sm 2 O 3 is contained in at least one of the parts by weight, the Cu-containing compound and the Sm-containing compound.
[0010]
The laminate of the present invention is a laminate having a conductor mainly composed of Ag and / or Cu inside and / or on the surface of a dielectric substrate formed by laminating a plurality of dielectric layers, wherein the dielectric layer comprises: The dielectric ceramic composition.
[0011]
[Action]
The dielectric ceramic composition of the present invention can be fired at a relatively low temperature of 900 to 1050 ° C., can have a high relative dielectric constant εr and Q value, and can have a relatively low temperature coefficient τf of a resonance frequency, and can be a laminated body (high frequency Electronic circuit boards and electronic components) can be reduced in size and performance.
[0012]
In the dielectric ceramic composition of the present invention, since at least one of the Cu-containing compound and the Sm-containing compound is contained in a total amount of 0.5 to 5 parts by weight in terms of CuO 2 and Sm 2 O 3 , the sintering process The shrinkage start temperature can be lowered to 820 ° C. or less, and it can be brought close to the shrinkage start temperature of the conductor. Even when the substrate or electronic component is simultaneously fired with the conductor mainly composed of Ag and Cu, Generation of warpage, distortion, and the like can be suppressed.
[0013]
DETAILED DESCRIPTION OF THE INVENTION
The dielectric ceramic composition of the present invention is a composite oxide containing Mg, Ca, and Ti as metal elements, and the composition formula based on the weight ratio of these metal element oxides is represented as aMgO · bCaO · cTiO 2. 100% by weight of main components represented by a, b, c: 25.0 ≦ a ≦ 35.0, 0.3 ≦ b ≦ 7.0, 60.0 ≦ c ≦ 70.0, a + b + c = 100 3 to 20 parts by weight of the B-containing compound in terms of B 2 O 3 and 1 to 10 parts by weight of the alkali metal-containing compound in terms of alkali metal carbonate with respect to parts, at least one of the Cu-containing compound and the Sm-containing compound Are contained in a total of 0.5 to 5 parts by weight in terms of CuO 2 and Sm 2 O 3 , respectively.
In the present invention, the MgO weight ratio a is 25 ≦ a ≦ 35 and the CaO weight ratio b is 0.3 ≦ b ≦ 7 when the MgO weight ratio a is less than 25 wt%. This is because, if the weight ratio b of CaO and CaO exceeds 7% by weight, the temperature coefficient τf of the resonance frequency becomes too large. Conversely, when the MgO weight ratio a exceeds 35% by weight or the CaO weight ratio b is less than 0.3% by weight, the temperature coefficient τf of the resonance frequency becomes too negative. . Therefore, the weight ratio a of MgO and the weight ratio b of CaO are specified as 25.0 ≦ a ≦ 35.0 and 0.3 ≦ b ≦ 7.0, and in particular, the temperature coefficient τf of the resonance frequency of the dielectric ceramic. From the viewpoint, 28.0 ≦ a ≦ 34.0 and 0.4 ≦ b ≦ 6.5 are preferable.
[0015]
The reason why the weight ratio c of TiO 2 is set to 60 ≦ c ≦ 70 is that the Q value decreases when the weight ratio c of TiO 2 is less than 60% by weight or more than 70% by weight. Therefore, the weight ratio c of TiO 2 is specified as 60 ≦ c ≦ 70, and 64 ≦ c ≦ 68 is particularly preferable from the viewpoint of the Q value of the dielectric ceramic.
[0016]
Further, by using MgTiO 3 and CaTiO 3 as starting materials, the Q value can be further improved and the temperature coefficient can be easily controlled. That, (100-x) MgTiO 3 · xCaTiO 3 ( however, where x represents the weight ratio, 1 ≦ x ≦ 15) with respect to 100 parts by weight of the main component represented by the B-containing compound B 2 O 3 to 3 parts by weight in terms of 3, 1 to 10 parts by weight in terms of alkali metal carbonates in terms of alkali metal carbonate , and at least one of Cu-containing compounds and Sm-containing compounds is 0 in total in terms of CuO 2 and Sm 2 O 3 , respectively. When 5 to 5 parts by weight are contained.
[0017]
Here, the weight ratio of CaTiO 3 in the main component was set to 1 ≦ x ≦ 15 because when the weight ratio of CaTiO 3 is less than 1% by weight, the temperature coefficient τf of the resonance frequency is greatly shifted to the minus side. In addition, when the weight ratio exceeds 15% by weight, the temperature coefficient τf of the resonance frequency is greatly shifted to the plus side. Therefore, the weight ratio x of CaTiO 3 is specified as 1 to 15% by weight, and in particular, 1 to 10% by weight is preferable from the viewpoint of the temperature coefficient τf of the resonance frequency of the dielectric ceramic.
[0018]
In the present invention, the B-containing compound is 3 to 20 parts by weight in terms of B 2 O 3 , the alkali metal-containing compound is 1 to 10 parts by weight in terms of alkali metal carbonate, Cu-containing compounds and A total of 0.5 to 5 parts by weight of at least one Sm-containing compound in terms of CuO 2 and Sm 2 O 3 is contained.
[0019]
Thus with respect to 100 parts by weight of the main component, B for containing compounds were added 3 to 20 parts by weight terms of B 2 O 3 is, 1100 ° C. in the case the addition amount of B 2 O 3 is less than 3 parts by weight However, it is not sintered and co-firing with Ag or Cu becomes impossible. Conversely, when it exceeds 20 parts by weight, the crystal phase changes and the Q value decreases. Therefore, the addition amount of the B-containing compound is specified as 3 to 20 parts by weight in terms of B 2 O 3 with respect to the main component, and particularly 3 to 9 parts by weight is desirable from the viewpoint of the Q value of the dielectric ceramic. B-containing compounds include metallic boron, B 2 O 3 , colemanite, CaB 2 O 4 and the like.
[0020]
In addition, 1 to 10 parts by weight of the alkali metal-containing compound was added in terms of alkali metal carbonate because the alkali metal-containing compound, for example, the Li-containing compound was added in an amount of less than 1 part by weight, even if sintered at 1100 ° C. In other words, co-firing with Ag or Cu becomes impossible, and conversely, when the amount exceeds 10 parts by weight, the crystal phase changes and the Q value decreases. Therefore, the addition amount of the alkali metal-containing compound is specified to be 1 to 10 parts by weight in terms of alkali metal carbonate, for example, Li 2 CO 3 with respect to 100 parts by weight of the main component, particularly in terms of the Q value of the dielectric ceramic. Is preferably 3 to 7 parts by weight.
[0021]
Examples of the alkali metal include Li, Na, and K. Among these, Li is particularly desirable. Examples of the alkali metal-containing compound include carbonates and oxides of the above alkali metals.
[0022]
In the dielectric ceramic composition of the present invention, a total of 0.5 to 5 parts by weight of CuO and Sm 2 O 3 in terms of at least one of the Cu-containing compound and the Sm-containing compound is contained with respect to 100 parts by weight of the main component. To do. When these are less than 0.5 parts by weight, the shrinkage start temperature in the sintering process of the dielectric ceramic is higher than 820 ° C., and the effect of addition cannot be obtained. On the other hand, if the additive exceeds 5 parts by weight, the dielectric constant εr or Q value of the dielectric ceramic decreases. From the viewpoint of the relative dielectric constant εr or Q value of the dielectric ceramic, a total of 1 to 4 parts by weight is desirable.
[0023]
In the present invention, an oxide such as Si, Zn, Mn, Zr, etc. may be added and contained within a range that does not adversely affect the dielectric properties. In this case, further low temperature firing is possible.
[0024]
The dielectric ceramic composition of the present invention may contain Al, Fe, Hf, and Sn as ball components and inevitable impurities. As the crystal phase, MgTiO 3 and CaTiO 3 are the main crystal phases, and (Mg, Ti) 2 (BO 3 ) O may precipitate. In the dielectric ceramic composition of the present invention, the average crystal grain size is 2 to 3 μm.
[0025]
In the dielectric ceramic composition of the present invention, for example, each raw material powder of MgCO 3 , CaCO 3 , and TiO 2 is weighed so as to be a predetermined amount, mixed and pulverized, and this is heated in the atmosphere at a temperature of 1100 to 1300 ° C. Calcinate for 1-3 hours. For example, each powder of B 2 O 3 and Li 2 CO 3 and at least one powder of CuO 2 and Sm 2 O 3 are weighed to a predetermined amount, mixed and pulverized, and pressed into the obtained calcined product. After forming into a predetermined shape by a known method such as molding or a doctor blade method, firing is performed at 900 to 1050 ° C. for 0.5 to 2.0 hours in an oxidizing atmosphere such as the air or a non-oxidizing atmosphere such as a nitrogen atmosphere. Can be obtained.
[0026]
The laminate of the present invention has a conductor mainly composed of Ag and / or Cu inside and / or on the surface of a dielectric substrate formed by laminating a plurality of dielectric layers. The dielectric ceramic composition described above is used.
[0027]
Examples of the conductor include those containing Ag and / or Cu as a main component, for example, Ag, Cu, or those obtained by adding a glass component, a ceramic component, or a metal such as Pt or Pd to Ag or Cu. A conductor in which a glass component or a ceramic component is added to these metals is preferably used as an inner conductor, and a conductor to which Pt or Pd is added is preferably used as a surface conductor. Such a conductor has a shrinkage start temperature at the time of firing of about 650 ° C. at the highest.
[0028]
The dielectric ceramic composition of the present invention, respectively CuO at least one kind of of the Cu-containing compound and Sm-containing compound, by containing total 0.5 to 5 parts by weight Sm 2 O 3 in terms of the shrinkage starting temperature 820 Since the temperature can be set to ° C. or lower, it is possible to approach the shrinkage start temperature of the conductor.
[0029]
【Example】
Example 1
First, MgCO of 99% pure 3, CaCO 3, each raw material powder of TiO 2 were weighed so that the amounts shown in Tables 1 and 2, 24 hours of pure water was added as a medium raw material powder, ZrO 2 After mixing with a ball mill using a ball, the mixture was dried, and then the dried product was calcined in the atmosphere at a temperature of 1200 ° C. for 1 hour.
[0030]
The resulting calcined product into B 2 O 3, Li 2 CO 3, Nb 2 O 5, CuO, a powder of Sm 2 O 3 were weighed so that the ratio shown in Table 1, 24 hours at the ball mill After mixing, 1% by weight of polyvinyl alcohol is added as a binder and granulated, and the granulated product is press-molded with a pressurizing force of about 1 t / cm 2 to form a cylindrical shape having a diameter of about 12 mm and a height of 10 mm. The body was molded.
[0031]
Thereafter, the molded body was heated in the atmosphere at a temperature of 400 ° C. for 4 hours to remove the binder, and subsequently fired in the atmosphere at each temperature shown in Tables 1 and 2 for 60 minutes. Both end surfaces of the cylindrical body thus obtained were polished to prepare a dielectric property evaluation sample.
[0032]
The evaluation of the dielectric characteristics is performed by using the evaluation sample by the dielectric cylindrical resonator method, setting the resonance frequency to 6-8 GHz, and setting the relative dielectric constant εr of each sample and 1 / tan δ at 7 GHz, that is, the Q value. In addition to the measurement, the temperature coefficient τf of the resonance frequency in the temperature range of −40 to + 85 ° C. was measured. These results are shown in Tables 1 and 2. In Tables 1 and 2, Sample No. Reference numerals 25 to 29 denote reference samples.
[0033]
[Table 1]
[Table 2]
According to Tables 1 and 2, in the dielectric ceramic composition of the present invention, the shrinkage start temperature in the sintering process is 800 to 820 ° C., the firing temperature is 900 to 1050 ° C., and the relative dielectric constant is further reduced. It can be seen that the ratio εr is 18 or more, the Q value at 7 GHz is 2000 or more, and the temperature coefficient τf of the resonance frequency is excellent within ± 40 ppm / ° C.
[0036]
Samples No. 13 and 14 used Na 2 CO 3 instead of Li 2 CO 3 .
[0037]
Example 2
First, each raw material powder of MgTiO 3 and CaTiO 3 having a purity of 99% or more is weighed so as to have the amounts shown in Tables 3 and 4, and pure water is added to the raw material powder as a medium, and ZrO 2 balls are used for 24 hours. After mixing in a ball mill, the mixture was dried, and then the dried product was calcined in the atmosphere at a temperature of 1200 ° C. for 1 hour.
[0038]
The resulting calcined product into B 2 O 3, Li 2 CO 3, Nb 2 O 5, CuO, a powder of Sm 2 O 3 were weighed so that the ratio shown in Table 3 and 4, for 24 hours at the ball mill After mixing, 1% by weight of polyvinyl alcohol is added as a binder and granulated, and the granulated product is press-molded with a pressurizing force of about 1 t / cm 2 to form a cylindrical shape having a diameter of about 12 mm and a height of 10 mm. The body was made.
[0039]
Thereafter, the molded body was heated in the atmosphere at a temperature of 400 ° C. for 4 hours to remove the binder, and subsequently fired in the atmosphere at each temperature shown in Tables 3 and 4 for 60 minutes. Both end surfaces of the cylindrical body thus obtained were polished to prepare a dielectric property evaluation sample. Dielectric properties were evaluated in the same manner as described above, and the results are shown in Tables 3 and 4. In Tables 3 and 4, Sample No. 21-25 show a reference sample.
[0040]
[Table 3]
[Table 4]
According to Tables 3 and 4, in the dielectric ceramic composition of the present invention, the shrinkage start temperature during the sintering process is 800 to 820 ° C., the firing temperature is 1050 ° C. or less, and the relative dielectric constant is further reduced. It can be seen that εr is 18 or more, the Q value is 3000 or more, and the temperature coefficient τf of the resonance frequency is within ± 30 ppm / ° C.
[0043]
【The invention's effect】
In the dielectric ceramic composition of the present invention, the shrinkage start temperature in the sintering process can be brought to 820 ° C. or less, which is close to the conductor shrinkage start temperature, and the firing temperature is 1050 ° C. or less. It is possible to obtain a laminate (substrate or electronic component) that can be fired simultaneously with Cu, Cu, and the like, and does not warp or distort even if fired simultaneously.
[0044]
Furthermore, it has a high relative dielectric constant (18 or more) in the high frequency region, a high Q value (2000 or more), and excellent temperature characteristics (within ± 40) of the resonance frequency. Further downsizing and high performance of parts can be realized.
Claims (3)
ａＭｇＯ・ｂＣａＯ・ｃＴｉＯ２
と表した時、前記ａ、ｂ、ｃが
２５．０≦ａ≦３５．０
０．３≦ｂ≦ ７．０
６０．０≦ｃ≦７０．０
ａ＋ｂ＋ｃ＝１００
を満足する主成分と、該主成分１００重量部に対して、Ｂ含有化合物をＢ２Ｏ３換算で３〜２０重量部、アルカリ金属含有化合物をアルカリ金属炭酸塩換算で１〜１０重量部、Ｃｕ含有化合物およびＳｍ含有化合物のうち少なくとも１種をそれぞれＣｕＯ、Ｓｍ２Ｏ３換算で合計０．５〜５重量部含有してなることを特徴とする誘電体磁器組成物。A composite oxide containing Mg, Ca, and Ti as metal elements, and the composition formula according to the weight ratio of these metal element oxides is aMgO · bCaO · cTiO 2
When a, b, c are 25.0 ≦ a ≦ 35.0
0.3 ≦ b ≦ 7.0
60.0 ≦ c ≦ 70.0
a + b + c = 100
The B-containing compound is 3 to 20 parts by weight in terms of B 2 O 3 and the alkali metal-containing compound is 1 to 10 parts by weight in terms of alkali metal carbonate, A dielectric ceramic composition comprising a total of 0.5 to 5 parts by weight of at least one of a Cu-containing compound and an Sm-containing compound in terms of CuO 2 and Sm 2 O 3 , respectively.
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|---|---|---|---|
| JP26006197A JP3793549B2 (en) | 1997-09-25 | 1997-09-25 | Dielectric porcelain composition and laminate |
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| JP26006197A JP3793549B2 (en) | 1997-09-25 | 1997-09-25 | Dielectric porcelain composition and laminate |
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| US7378363B2 (en) * | 2005-05-20 | 2008-05-27 | Skyworks Solutions, Inc. | Dielectric ceramic composition having wide sintering temperature range and reduced exaggerated grain growth |
| JP5197559B2 (en) * | 2009-12-11 | 2013-05-15 | 京セラ株式会社 | High frequency dielectric ceramic composition and dielectric resonator using the same |
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