JP3631607B2 - High frequency dielectric ceramics and laminates - Google Patents
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Description
【０００１】
【発明の属する技術分野】
本発明は、マイクロ波、ミリ波等の高周波領域において、高いＱ値を有する高周波用誘電体磁器および積層体に関するものであり、例えば、マイクロ波やミリ波などの高周波領域において使用される種々の共振器用材料やＭＩＣ用誘電体基板材料、誘電体導波路用材料、積層型セラミックコンデンサの誘電体層等に用いることができる高周波用誘電体磁器および積層体に関する。
【０００２】
【従来技術】
従来、誘電体磁器は、マイクロ波やミリ波等の高周波領域において誘電体共振器、ＭＩＣ用誘電体基板や導波路等に広く利用されている。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１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、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±４０ｐｐｍ／℃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では焼結温度がまだ高く、さらに焼結における収縮開始温度が８４５〜９６０℃と高温であるため、導体材料との収縮挙動のマッチングが悪く、焼成された基板や電子部品が反る、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、基板等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、焼成温度をさらに低下させることができるとともに、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を抑制できる高周波用誘電体磁器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】
本発明の高周波用誘電体磁器は、低損失セラミックフィラー１００重量部と、該低損失セラミックフィラー１００重量部に対して、Ｂ、アルカリ金属、Ｓｉおよびアルカリ土類金属を含有する粒界相形成成分５〜３０重量部とからなる組成物を焼成してなり、Ｑ値とその測定周波数との積で表されるＱｆ値が２００００〔ＧＨｚ〕以上のものである。
【０００９】
ここで、粒界相形成成分は、重量比による組成式を、ａＢ２ Ｏ３ ・ｂＡ２ Ｏ・ｃＳｉＯ２ ・ｄＲＯと表した時、前記ａ、ｂ、ｃおよびｄが、４０≦ａ≦９０、８≦ｂ≦２０、１≦ｃ≦２０、１≦ｄ≦２０、ａ＋ｂ＋ｃ＋ｄ＝１００を満足することが望ましい。ここで、Ａはアルカリ金属のうち少なくとも一種以上、Ｒはアルカリ土類金属のうち少なくとも一種以上である。
【００１０】
また、低損失セラミックフィラーは、単体でのＱｆ値が３００００〔ＧＨｚ〕以上であることが望ましい。さらに、低損失セラミックフィラーは、少なくともＭｇとＴｉを含有するペロブスカイト型結晶粒子、もしくはＢａＴｉ４ Ｏ９ 粒子であることが望ましい。
【００１２】
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高周波用誘電体磁器からなるものである。
【００１３】
【作用】
本発明の高周波用誘電体磁器は、Ｂ、アルカリ金属、Ｓｉおよびアルカリ土類金属を含有する粒界相形成成分により、低損失セラミックフィラー自体のＱｆ値をそれほど低下させることなく、９２０℃以下の焼成温度で焼成できるとともに、収縮開始温度を８３０℃以下にでき、Ａｇ、Ｃｕ等の内部導体と同時焼成しても変形することがなく、さらに、Ｑ値とその測定周波数との積で表される磁器のＱｆ値が２００００〔ＧＨｚ〕以上となり、共振器用材料やＭＩＣ用誘電体基板材料、誘電体導波路用材料、積層型セラミックコンデンサの誘電体層等に好適に用いることができる。
【００１４】
また、粒界相形成成分が、重量比による組成式をａＢ２ Ｏ３ ・ｂＡ２ Ｏ・ｃＳｉＯ２ ・ｄＲＯ（Ａはアルカリ金属のうち少なくとも一種、Ｒはアルカリ土類金属のうち少なくとも一種）と表した時、ａ、ｂ、ｃおよびｄが、４０≦ａ≦９０、８≦ｂ≦２０、１≦ｃ≦２０、１≦ｄ≦２０、ａ＋ｂ＋ｃ＋ｄ＝１００を満足することにより、９２０℃以下の焼成温度で焼成できるとともに、焼成収縮開始温度を８３０℃以下にすることができ、Ａｇおよび／またはＣｕを主成分とする導体の収縮開始温度に近づけることができ、Ａｇ、Ｃｕを主成分とする導体と同時焼成した場合でも、基板や電子部品の反りや歪み等の発生を抑制することができ、さらに、共振周波数の温度係数τｆを±４０ｐｐｍ／℃の範囲内とすることが可能となる。
【００１５】
さらに、低損失セラミックフィラー単体でのＱｆ値を３００００以上とすることにより、磁器のＱｆ値を確実に２００００以上にできる。特に、低損失セラミックフィラーを、少なくともＭｇとＴｉを含有するペロブスカイト型結晶粒子、もしくはＢａＴｉ４ Ｏ９ 粒子とすることにより、低損失セラミックフィラーのＱｆ値を高くすることができ、磁器の高Ｑｆ値化を促進できる。
【００１７】
本発明の積層体では、上記したような誘電体磁器を用いることにより、Ａｇ、Ｃｕを主成分とする導体と同時焼成した場合でも、積層体のそり、歪み等の発生を抑制でき、マイクロ波やミリ波等の高周波領域において、共振器、ＭＩＣ用基板、導波路用として好適に使用できる。
【００１８】
【発明の実施の形態】
本発明の高周波用誘電体磁器は、低損失セラミックフィラー１００重量部と、該低損失セラミックフィラー１００重量部に対して、Ｂ、アルカリ金属、Ｓｉおよびアルカリ土類金属を含有する粒界相形成成分５〜３０重量部とからなる組成物を焼成してなり、Ｑ値とその測定周波数との積で表されるＱｆ値が２００００〔ＧＨｚ〕以上のものである。
【００１９】
ここで、低損失セラミックフィラーとしては、フィラー単独でのＱｆ値が３００００〔ＧＨｚ〕以上であることが望ましい。例えば、モル比による組成式（１−ｘ）ＭｇＴｉＯ３ ・ｘＣａＴｉＯ３ （０≦ｘ≦０．２）で表される少なくともＭｇとＴｉを含有するペロブスカイト型結晶粒子や、ＢａＴｉ４ Ｏ９ 粒子が望ましい。
【００２０】
Ｂ、アルカリ金属、Ｓｉおよびアルカリ土類金属を含有する粒界相形成成分を用いたのは、これらの成分を用いることにより、焼成温度を９２０℃以下とすることができるとともに、焼成収縮開始温度を８３０℃以下とでき、磁器としてのＱｆ値を２００００〔ＧＨｚ〕以上とすることができるからである。
【００２１】
粒界相形成成分量を、低損失セラミックフィラー１００重量部に対して５〜３０重量部としたのは、５重量部未満の場合には、焼成温度を低下させる効果が小さく、ＡｇまたはＣｕを主成分とする導体と同時焼成ができなくなり、逆に３０重量部を越える場合には、誘電体磁器の共振周波数の温度係数τｆがプラス側に大きくなりすぎてしまう。とりわけ誘電体磁器の焼結性と共振周波数の温度係数τｆの観点から添加量は、１５〜２５重量部が好ましい。
【００２２】
粒界相形成成分としては、重量比による組成式をａＢ２ Ｏ３ ・ｂＡ２ Ｏ・ｃＳｉＯ２ ・ｄＲＯ（Ａはアルカリ金属の少なくとも一種、Ｒはアルカリ土類金属の少なくとも一種）と表した時、ａ、ｂ、ｃおよびｄが、４０≦ａ≦９０、８≦ｂ≦２０、１≦ｃ≦２０、１≦ｄ≦２０、ａ＋ｂ＋ｃ＋ｄ＝１００を満足することが望ましい。
【００２３】
ここで、Ｂ２ Ｏ３ 量ａを４０≦ａ≦９０としたのは、ａが４０重量％未満の場合は焼成温度を低下させる効果が小さく、ＡｇまたはＣｕを主成分とする導体と同時焼成ができなくなり、逆に９０重量％を越える場合には、焼結体中のガラス相の割合が増加してＱ値が低下するからである。よって、焼結性を維持し、高いＱ値を得るという観点から６０≦ａ≦７５重量％が望ましい。
【００２４】
また、Ａ２ Ｏ量ｂを８≦ｂ≦２０重量％としたのは、ｂが８重量％未満の場合には、焼成温度を低下させる効果が小さく、ＡｇまたはＣｕを主成分とする導体と同時焼成ができなくなり、逆に２０重量％を越える場合には、結晶相が変化してＱ値が低下するからである。誘電体磁器のＱ値の観点から１３≦ｂ≦１８重量％が望ましい。ここで、Ａはアルカリ金属のうち少なくとも一種であり、アルカリ金属としてはＬｉ、Ｎａ、Ｋがあるが、特にＬｉが望ましい。
【００２５】
さらに、ＳｉＯ２ 量ｃを１≦ｃ≦２０重量％としたのは、ｃが１重量％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８３０℃よりも高くなり、添加効果が得られないからである。一方、２０重量％を越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、ｃは４≦ｃ≦８重量％が望ましい。
【００２６】
さらにまた、ＲＯ量ｄを１≦ｄ≦２０重量％としたのは、ｄが１重量％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８３０℃よりも高くなり、添加効果が得られない。一方、２０重量％を越えると誘電体磁器の共振周波数の温度係数τｆがプラス側に大きくなりすぎてしまう。とりわけ誘電体磁器の焼結性と共振周波数の温度係数τｆの観点からはｄは、５≦ｄ≦１５重量％が好ましい。ここで、Ｒはアルカリ土類金属のうち少なくとも一種であり、アルカリ土類金属としてはＢｅ、Ｍｇ、Ｃａ、Ｓｒ、Ｂａ等があるが、このうちＢａが望ましい。
【００２７】
本発明の高周波用誘電体磁器は、主成分が、モル比による組成式を（１−ｘ）ＭｇＴｉＯ３ ・ｘＣａＴｉＯ３ と表した時、ｘが０≦ｘ≦０．２を満足することが望ましい。ここで、ｘを０≦ｘ≦０．２としたのは、ｘが０．２モルを越える場合には、共振周波数の温度係数τｆがプラス側に大きくなりすぎてしまうからである。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ｘは０．０３≦ｘ≦０．１３が好ましい。また、ＭｇＴｉＯ３ とＣａＴｉＯ３ において、Ｍｇ／Ｔｉ比またはＣａ／Ｔｉ比が０．９〜１．１の範囲であれば、本発明の磁器の主成分として使用できる。
【００２８】
そして、本発明の高周波用誘電体磁器では、上記主成分１００重量部に対して、ＢをＢ２ Ｏ３ 換算で３〜２０重量部、アルカリ金属をアルカリ金属炭酸塩換算で１〜１０重量部、ＳｉをＳｉＯ２ 換算で０．０１〜５重量部、さらにアルカリ土類金属をアルカリ土類金属酸化物換算で０．１〜５重量部含有するものである。
【００２９】
ここで、ＢをＢ２ Ｏ３ 換算で３〜２０重量部含有したのは、Ｂが３重量部未満の場合には１１００℃でも焼結せず、ＡｇまたはＣｕを主成分とする導体と同時焼成ができなくなり、逆に２０重量部を越える場合には焼結体中のガラス相の割合が増加してＱ値が低下するからである。よって、焼結性を維持し、高いＱ値を得るという観点からＢ２ Ｏ３ 換算で５〜１５重量部含有することが望ましい。Ｂ含有化合物としては、金属硼素、Ｂ２ Ｏ３ 、コレマイト、ＣａＢ２ Ｏ４ 、ホウケイ酸ガラス、ホウケイ酸アルカリガラス、ホウケイ酸アルカリ土類ガラス等がある。
【００３０】
また、アルカリ金属をアルカリ金属炭酸塩換算で１〜１０重量部含有したのは、含有量が１重量部未満の場合には１１００℃でも焼結せず、ＡｇまたはＣｕを主成分とする導体と同時焼成ができなくなり、逆に１０重量部を越える場合には結晶相が変化してＱ値が低下するからである。誘電体磁器のＱ値の観点から４〜９重量部が望ましい。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。
【００３１】
さらに、ＳｉをＳｉＯ２ 換算で０．０１〜５重量部含有したのは、含有量が０．０１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約８４０℃と高く、添加効果が得られないからである。一方、５重量部を越えると比誘電率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０．５〜３重量部が望ましい。Ｓｉ含有化合物としてはＳｉＯ２ 、ＭｇＳｉＯ３ 等がある。
【００３２】
また、アルカリ土類金属をアルカリ土類金属酸化物換算で０．１〜５重量部含有するものである。これらが０．１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８３０℃よりも高く、添加効果が得られない。一方、５重量部を越えると誘電体磁器の共振周波数の温度係数τｆがプラス側に大きくなりすぎてしまう。とりわけ誘電体磁器の焼結性と共振周波数の温度係数τｆの観点からは合計０．５〜３．５重量部が好ましい。
【００３３】
アルカリ土類金属としては、Ｍｇ、Ｃａ、Ｓｒ、Ｂａがあり、このなかでもＢａが望ましい。アルカリ土類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。
【００３４】
さらに、本発明の高周波用誘電体磁器では、焼結性を改善する点から、主成分１００重量部に対して、さらにＭｎをＭｎＯ２ 換算で０．１〜３重量部含有することが望ましい。ＭｎをＭｎＯ２ 換算で０．１〜３重量部含有せしめたのは、０．１重量部よりも少ない場合にはその添加効果がなく、さらに３重量部よりも多い場合には誘電特性が悪化するからである。ＭｎはＭｎＯ２ 換算で１．２〜１．８重量部含有することが望ましい。
【００３５】
本発明の高周波用誘電体磁器は、原料粉末として、例えば、ＭｇＴｉＯ３ 粉末、ＣａＴｉＯ３ 粉末、およびＢ２ Ｏ３ 粉末、Ｌｉ２ ＣＯ３ 粉末、ＳｉＯ２ 粉末、ＭｎＯ２ 粉末、さらにアルカリ土類金属酸化物（ＭｇＯ、ＣａＯ、ＳｒＯ、ＢａＯ）粉末を準備し、これらを上記組成比となるように秤量し、ＺｒＯ２ ボールにより粉砕混合し、この混合粉末を６５０〜８５０℃で仮焼した後、再度ＺｒＯ２ ボールにより粉砕粒径が２．５μｍ以下になるまで粉砕混合し、この仮焼粉末をプレス成形やドクターブレード法等の公知の方法により所定形状に成形し、大気中または酸素雰囲気中または窒素雰囲気等の非酸化性雰囲気において９２０℃以下、特に８７０〜９２０℃で０．５〜２時間焼成することにより得られる。原料粉末は、焼成により酸化物を生成する水酸化物、炭酸塩、硝酸塩等の金属塩を用いても良い。
【００３６】
アルカリ土類金属は、Ｂ、Ｌｉ、Ｓｉを含むガラスフリットとして添加することが焼結性向上の点から望ましい。この場合には、Ｂ、Ｌｉ、Ｓｉ量は、ガラスフリットに含有される量と、粉末として添加される量の合計量となる。
【００３７】
本発明の高周波用誘電体磁器では、原料の混合粉砕工程等の製造過程で、Ｚｒ、Ａｌ等が混入したり、原料の不可避不純物として、Ａｌ、Ｆｅ、Ｈｆ、Ｓｎ等が含まれることもある。
【００３８】
また、本発明の高周波用誘電体磁器では、例えば、結晶相として、ＭｇＴｉＯ３ とＣａＴｉＯ３ を主結晶相とし、（Ｍｇ，Ｔｉ）２ （ＢＯ３ ）Ｏが析出することもある。尚、アルカリ土類金属は、ＭｇＴｉＯ３ とＣａＴｉＯ３ のＡサイトに固溶したり、あるいはガラス成分となって、焼結性を向上させることになる。また、Ｓｉはガラス相として存在する。さらに、本発明の高周波用誘電体磁器では平均結晶粒径が１〜５μｍのものである。
【００３９】
【実施例】
実施例１
原料として純度９９％以上の、Ｂ２ Ｏ３ 、Ｌｉ２ ＣＯ３ 、ＳｉＯ２ 粉末、さらにアルカリ土類酸化物としてＭｇＯ、ＣａＯ、ＳｒＯ、ＢａＯ粉末を用い、表１に示す割合となるように秤量し、純水を媒体とし、モル比０．９５ＭｇＴｉＯ３ ・０．０５ＣａＴｉＯ３ （Ｑｆ値１０００００）またはＢａＯ・４．０ＴｉＯ２ （Ｑｆ値５００００）で表される低損失セラミックフィラー成分と、ＺｒＯ２ ボールを用いたボ−ルミルにて２０時間湿式混合した。次にこの混合物を乾燥（脱水）し、８００℃で１時間仮焼した。この仮焼物を、粉砕粒径が１．０μｍ以下になるように粉砕し、誘電特性評価用の試料として直径１０ｍｍ高さ８ｍｍの円柱状に１ｔｏｎ／ｃｍ２ の圧力でプレス成形し、これを表１に示す温度で２時間焼成し、直径８ｍｍ、高さ６ｍｍの円柱状の試料を得た。この際、熱収縮の測定により、収縮開始温度を測定した。
【００４０】
誘電特性の評価は、前記試料を用いて誘電体円柱共振器法にて周波数８ＧＨｚにおける比誘電率とＱ値を測定した。Ｑ値と測定周波数ｆとの積で表されるＱｆ値を表１に記載した。さらに、−４０〜＋８５℃の温度範囲における共振周波数の温度係数τｆ〔ｐｐｍ／℃〕を測定した。その結果を表１に記載した。
【００４１】
【表１】
この表１から、本発明の誘電体磁器は、比誘電率が１８〜４０、Ｑｆ値が２００００〔ＧＨｚ〕以上、かつ、共振周波数の温度係数τｆが±４０ｐｐｍ／℃以内の優れた誘電特性を有するとともに、７６０〜８３０℃で焼結収縮が開始し、９２０℃以下で焼成が可能な優れた焼結性を有していることが判る。
【００４３】
尚、アルカリ金属としては、試料Ｎo.４でＮａを、Ｎo.８でＫを用い、その他はＬｉを用いた。また、アルカリ土類金属としては、試料Ｎo.１０でＣａを、Ｎo.１１でＭｇを、Ｎo.１２でＢａを、Ｎo.１３でＳｒを用い、その他ではＢａとＣａを用いた。この際ＢａＯとＣａＯの重量比を１：１とした。尚、試料Ｎｏ．１３は参考試料である。
【００４４】
実施例２
原料として純度９９％以上の、ＭｇＴｉＯ３ 粉末、ＣａＴｉＯ３ 粉末、Ｂ２ Ｏ３ 粉末、アルカリ金属炭酸塩粉末（Ｌｉ２ ＣＯ３ 、Ｎａ２ ＣＯ３ 、Ｋ２ ＣＯ３ ）、ＳｉＯ２ 粉末、ＭｎＯ２ 粉末、さらにアルカリ土類酸化物粉末（ＭｇＯ、ＣａＯ、ＳｒＯ、ＢａＯ）を、表２に示す割合となるように秤量し、純水を媒体とし、ＺｒＯ２ ボールを用いたボールミルにて２０時間湿式混合した。次にこの混合物を乾燥（脱水）し、８００℃で１時間仮焼した。
【００４５】
この仮焼物を、粉砕粒径が１．０μｍ以下になるように粉砕し、誘電特性評価用の試料として直径１０ｍｍ高さ８ｍｍの円柱状に１ｔｏｎ／ｃｍ２ の圧力でプレス成形し、これを表３に示す温度で３時間焼成し、直径８ｍｍ、高さ６ｍｍの円柱状の試料を得た。
【００４６】
誘電特性の評価は、前記試料を用いて誘電体円柱共振器法にて周波数８ＧＨｚにおける比誘電率とＱ値を測定した。Ｑ値と測定周波数ｆとの積で表されるＱｆ値を表３に記載した。さらに、−４０〜＋８５℃の温度範囲における共振周波数の温度係数τｆ〔ｐｐｍ／℃〕を測定した。その結果を表３に記載した。尚、試料Ｎｏ．３２は参考試料である。
【００４７】
【表２】
【表３】
これらの表２、３から、本発明の誘電体磁器組成物は、比誘電率が１８〜２０、Ｑｆ値が２００００〔ＧＨｚ〕以上、かつ、共振周波数の温度係数τｆが±４０ｐｐｍ／℃以内の優れた誘電特性を有するとともに、７６０〜８３０℃で焼結収縮が開始し、９２０℃以下で焼成が可能な優れた焼結性を有していることが判る。
【００５０】
尚、表１のアルカリの欄において、Ｌｉ、Ｎａ、Ｋと記載したが、これはＬｉ２ ＣＯ３ 、Ｎａ２ ＣＯ３ 、Ｋ２ ＣＯ３ の意味であり、また、アルカリ土類の欄において、Ｍｇ、Ｂａ、Ｃａ、Ｓｒと記載したが、これは、ＭｇＯ、ＣａＯ、ＳｒＯ、ＢａＯの意味である。さらに、表１の試料Ｎｏ．２４、２５については、Ｍｇ／Ｔｉ、Ｃａ／Ｔｉ比がそれぞれ１．１、０．９の原料粉末を用いた。
【００５１】
【発明の効果】
本発明によれば、焼成温度を９２０℃以下に、収縮開始温度を８３０℃以下とすることが可能となるため、ＡｇやＣｕ等の導体金属と同時に焼成でき、その際導体金属の収縮挙動のミスマッチから発生する基板の反りや歪みが抑制されるとともに、高周波領域において２００００以上のＱｆ値を有するため、電子部品や基板の小型・高性能化が実現できる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a high frequency dielectric ceramic having a high Q value in a high frequency region such as a microwave and a millimeter wave, and a laminated body. For example, the present invention relates to various types used in a high frequency region such as a microwave and a millimeter wave. The present invention relates to high-frequency dielectric ceramics and laminates that can be used for resonator materials, MIC dielectric substrate materials, dielectric waveguide materials, dielectric layers of multilayer ceramic capacitors, and the like.
[0002]
[Prior art]
2. Description of the Related Art Conventionally, dielectric ceramics are widely used for dielectric resonators, MIC dielectric substrates, waveguides, and the like in high frequency regions such as microwaves and millimeter waves. 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 a large conduction resistance, the conventional electronic circuit board has a problem that the Q value of the resonance circuit and the inductance is reduced, and the transmission loss of the conductor line is increased.
[0004]
Therefore, 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 the inner conductors such as Ag and 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 the 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 ppm / ° C., 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 JP-A-8-208330 has a high sintering temperature and the shrinkage start temperature in sintering is as high as 845 to 960 ° C., the shrinkage behavior with the conductor material. There are problems such as poor matching, and the fired substrate and electronic parts are warped and distorted.
[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 at the time of firing, there is a large difference from the shrinkage start temperature of the dielectric ceramic composition, thereby causing problems such as deformation of the substrate and the like. there were.
[0007]
The present invention has been made in view of the above problems, and can further reduce the firing temperature, lower the shrinkage start temperature, and can approach the shrinkage start temperature of the conductor, and is mainly composed of Ag or Cu. An object of the present invention is to provide a dielectric ceramic for high frequency and a laminate capable of suppressing warpage and distortion even when fired simultaneously with a conductor.
[0008]
[Means for Solving the Problems]
The dielectric ceramic for high frequency of the present invention comprises 100 parts by weight of a low-loss ceramic filler, and a grain boundary phase-forming component containing B, alkali metal, Si and alkaline earth metal with respect to 100 parts by weight of the low-loss ceramic filler A composition comprising 5 to 30 parts by weight is fired, and the Qf value represented by the product of the Q value and the measurement frequency is 20000 [GHz] or more.
[0009]
Here, the grain boundary phase-forming components, when the composition formula by weight, expressed as aB 2 O 3 · bA 2 O · cSiO 2 · dRO, wherein a, b, c and d, 40 ≦ a ≦ 90 8 ≦ b ≦ 20, 1 ≦ c ≦ 20, 1 ≦ d ≦ 20, and a + b + c + d = 100 are preferably satisfied. Here, A is at least one or more of alkali metals, and R is at least one or more of alkaline earth metals.
[0010]
Moreover, it is desirable that the low-loss ceramic filler has a single Qf value of 30000 [GHz] or more. Further, the low-loss ceramic filler is desirably perovskite-type crystal particles containing at least Mg and Ti, or BaTi 4 O 9 particles.
[0012]
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: It consists of the above-mentioned dielectric ceramic for high frequency.
[0013]
[Action]
The dielectric ceramic for high frequency of the present invention has a grain boundary phase-forming component containing B, alkali metal, Si, and alkaline earth metal, and does not lower the Qf value of the low-loss ceramic filler itself so much as 920 ° C. or less. It can be fired at the firing temperature, and the shrinkage start temperature can be made 830 ° C. or less. It does not deform even when fired simultaneously with an internal conductor such as Ag and Cu, and is further expressed by the product of the Q value and its measurement frequency. The Qf value of the ceramics is 20000 [GHz] or more, and can be suitably used for resonator materials, MIC dielectric substrate materials, dielectric waveguide materials, dielectric layers of multilayer ceramic capacitors, and the like.
[0014]
Further, the grain boundary phase forming component, aB 2 O 3 · bA 2 O · cSiO 2 · dRO the formula by weight ratio (A is at least one of an alkali metal, R represents at least one kind of alkaline earth metal) and When a, b, c and d satisfy 40 ≦ a ≦ 90, 8 ≦ b ≦ 20, 1 ≦ c ≦ 20, 1 ≦ d ≦ 20, a + b + c + d = 100, It can be fired at the firing temperature, the firing shrinkage start temperature can be 830 ° C. or less, can be close to the shrinkage start temperature of a conductor mainly composed of Ag and / or Cu, and Ag and Cu are the major components. Even in the case of simultaneous firing with the conductor, it is possible to suppress the occurrence of warpage, distortion, etc. of the substrate and electronic components, and it is possible to set the temperature coefficient τf of the resonance frequency within the range of ± 40 ppm / ° C.
[0015]
Further, by setting the Qf value of the low-loss ceramic filler alone to 30000 or more, the Qf value of the porcelain can be surely set to 20000 or more. In particular, when the low-loss ceramic filler is perovskite-type crystal particles containing at least Mg and Ti, or BaTi 4 O 9 particles, the Qf value of the low-loss ceramic filler can be increased, and the high Qf value of porcelain can be increased. Can be promoted.
[0017]
In the laminate of the present invention, by using the dielectric ceramic as described above, it is possible to suppress the occurrence of warpage, distortion, etc. of the laminate even when simultaneously fired with a conductor mainly composed of Ag and Cu. In a high frequency region such as a millimeter wave or a millimeter wave, it can be suitably used as a resonator, a substrate for MIC, and a waveguide.
[0018]
DETAILED DESCRIPTION OF THE INVENTION
The dielectric ceramic for high frequency of the present invention comprises 100 parts by weight of a low-loss ceramic filler, and a grain boundary phase-forming component containing B, alkali metal, Si and alkaline earth metal with respect to 100 parts by weight of the low-loss ceramic filler A composition comprising 5 to 30 parts by weight is fired, and the Qf value represented by the product of the Q value and the measurement frequency is 20000 [GHz] or more.
[0019]
Here, as a low loss ceramic filler, it is desirable that the Qf value of the filler alone is 30000 [GHz] or more. For example, a perovskite-type crystal grains containing at least Mg and Ti represented by the composition formula by molar ratio (1-x) MgTiO 3 · xCaTiO 3 (0 ≦ x ≦ 0.2), is desirable BaTi 4 O 9 particles .
[0020]
The grain boundary phase forming component containing B, alkali metal, Si and alkaline earth metal was used, and by using these components, the firing temperature could be 920 ° C. or lower, and the firing shrinkage start temperature This is because the Qf value as a porcelain can be 20000 [GHz] or more.
[0021]
The amount of the grain boundary phase forming component is 5 to 30 parts by weight with respect to 100 parts by weight of the low-loss ceramic filler. When the amount is less than 5 parts by weight, the effect of lowering the firing temperature is small. Simultaneous firing with the conductor as the main component becomes impossible, and conversely, when it exceeds 30 parts by weight, the temperature coefficient τf of the resonance frequency of the dielectric ceramic becomes too large on the plus side. In particular, the addition amount is preferably 15 to 25 parts by weight from the viewpoint of the sinterability of the dielectric ceramic and the temperature coefficient τf of the resonance frequency.
[0022]
When a grain boundary phase-forming components, aB 2 O 3 · bA 2 O · cSiO 2 · dRO the formula by weight ratio (A is at least one alkali metal, R represents at least one alkaline earth metal) expressed as , A, b, c, and d preferably satisfy 40 ≦ a ≦ 90, 8 ≦ b ≦ 20, 1 ≦ c ≦ 20, 1 ≦ d ≦ 20, and a + b + c + d = 100.
[0023]
Here, the amount of B 2 O 3 is set to 40 ≦ a ≦ 90 because the effect of lowering the firing temperature is small when a is less than 40% by weight, and co-firing with a conductor mainly composed of Ag or Cu. This is because when the amount exceeds 90% by weight, the ratio of the glass phase in the sintered body increases and the Q value decreases. Therefore, 60 ≦ a ≦ 75 wt% is desirable from the viewpoint of maintaining sinterability and obtaining a high Q value.
[0024]
In addition, the amount of A 2 O b is set to 8 ≦ b ≦ 20% by weight because when b is less than 8% by weight, the effect of lowering the firing temperature is small, and the conductor mainly composed of Ag or Cu This is because the simultaneous firing cannot be performed and, on the contrary, when the content exceeds 20% by weight, the crystal phase changes and the Q value decreases. From the viewpoint of the Q value of the dielectric ceramic, 13 ≦ b ≦ 18% by weight is desirable. Here, A is at least one of alkali metals, and examples of the alkali metal include Li, Na, and K. Li is particularly desirable.
[0025]
Furthermore, the SiO 2 content c is set to 1 ≦ c ≦ 20 wt% when the c is less than 1 wt%, the shrinkage start temperature in the sintering process of the dielectric ceramic becomes higher than 830 ° C. It is because it cannot be obtained. On the other hand, if the content exceeds 20% 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, c is preferably 4 ≦ c ≦ 8% by weight.
[0026]
Furthermore, the RO amount d is set to 1 ≦ d ≦ 20% by weight. When d is less than 1% by weight, the shrinkage start temperature in the sintering process of the dielectric ceramic becomes higher than 830 ° C. Cannot be obtained. On the other hand, if it exceeds 20% by weight, the temperature coefficient τf of the resonance frequency of the dielectric ceramic becomes too large on the plus side. In particular, from the viewpoint of the sinterability of the dielectric ceramic and the temperature coefficient τf of the resonance frequency, d is preferably 5 ≦ d ≦ 15% by weight. Here, R is at least one of alkaline earth metals, and examples of alkaline earth metals include Be, Mg, Ca, Sr, Ba, and the like, among which Ba is desirable.
[0027]
High-frequency dielectric ceramic of the present invention, the main component is, when representing the formula by molar ratio (1-x) MgTiO 3 · xCaTiO 3, it is desirable that x satisfies 0 ≦ x ≦ 0.2 . Here, x is set to 0 ≦ x ≦ 0.2 because when x exceeds 0.2 mol, the temperature coefficient τf of the resonance frequency becomes too large on the plus side. In particular, from the viewpoint of the temperature coefficient τf of the resonance frequency of the dielectric ceramic, x is preferably 0.03 ≦ x ≦ 0.13. Further, in the MgTiO 3 and CaTiO 3, be in the range of Mg / Ti ratio or Ca / Ti ratio is 0.9 to 1.1, can be used as the main component of the ceramic of the present invention.
[0028]
In the high frequency dielectric ceramic of the present invention, B is 3 to 20 parts by weight in terms of B 2 O 3 and alkali metal is 1 to 10 parts by weight in terms of alkali metal carbonate with respect to 100 parts by weight of the main component. , Si is contained in an amount of 0.01 to 5 parts by weight in terms of SiO 2 , and further an alkaline earth metal in an amount of 0.1 to 5 parts by weight in terms of an alkaline earth metal oxide.
[0029]
Here, B is contained in an amount of 3 to 20 parts by weight in terms of B 2 O 3 when B is less than 3 parts by weight, it does not sinter even at 1100 ° C., and at the same time as a conductor mainly composed of Ag or Cu. This is because when firing is impossible and, on the contrary, the amount exceeds 20 parts by weight, the ratio of the glass phase in the sintered body increases and the Q value decreases. Therefore, it is desirable to contain 5 to 15 parts by weight in terms of B 2 O 3 from the viewpoint of maintaining sinterability and obtaining a high Q value. Examples of the B-containing compound include metal boron, B 2 O 3 , collimite, CaB 2 O 4 , borosilicate glass, borosilicate alkali glass, and borosilicate alkaline earth glass.
[0030]
In addition, 1 to 10 parts by weight of alkali metal in terms of alkali metal carbonate is contained in the case where the content is less than 1 part by weight. This is because simultaneous firing cannot be performed, and conversely, when the amount exceeds 10 parts by weight, the crystal phase changes and the Q value decreases. From the viewpoint of the Q value of the dielectric ceramic, 4 to 9 parts by weight is desirable. 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.
[0031]
Furthermore, Si is contained in an amount of 0.01 to 5 parts by weight in terms of SiO 2 when the content is less than 0.01 parts by weight, the shrinkage start temperature in the sintering process of the dielectric ceramic is about 840 ° C. This is because the addition effect cannot be obtained. On the other hand, if it exceeds 5 parts by weight, the relative dielectric constant εr or the Q value decreases. From the viewpoint of the relative dielectric constant εr or Q value of the dielectric ceramic, 0.5 to 3 parts by weight is desirable. Examples of the Si-containing compound include SiO 2 and MgSiO 3 .
[0032]
Moreover, 0.1-5 weight part of alkaline-earth metal is contained in conversion of alkaline-earth metal oxide. When these are less than 0.1 parts by weight, the shrinkage start temperature in the sintering process of the dielectric ceramic is higher than 830 ° C., and the addition effect cannot be obtained. On the other hand, when the amount exceeds 5 parts by weight, the temperature coefficient τf of the resonance frequency of the dielectric ceramic becomes too large on the plus side. In particular, from the viewpoint of the sinterability of the dielectric ceramic and the temperature coefficient τf of the resonance frequency, the total amount is preferably 0.5 to 3.5 parts by weight.
[0033]
Examples of the alkaline earth metal include Mg, Ca, Sr, and Ba, and Ba is preferable among them. Examples of the alkaline earth metal-containing compound include carbonates and oxides of the above alkali metals.
[0034]
Furthermore, in the high frequency dielectric ceramic according to the present invention, it is desirable to further contain 0.1 to 3 parts by weight of Mn in terms of MnO 2 with respect to 100 parts by weight of the main component from the viewpoint of improving the sinterability. When Mn is added in an amount of 0.1 to 3 parts by weight in terms of MnO 2 , the effect is not added when the amount is less than 0.1 part by weight, and the dielectric property is deteriorated when the amount is more than 3 parts by weight. Because it does. It is desirable to contain 1.2 to 1.8 parts by weight of Mn in terms of MnO 2 .
[0035]
The dielectric ceramic for high frequency of the present invention includes, for example, MgTiO 3 powder, CaTiO 3 powder, B 2 O 3 powder, Li 2 CO 3 powder, SiO 2 powder, MnO 2 powder, and alkaline earth metal as raw material powder. After preparing oxide (MgO, CaO, SrO, BaO) powders, these were weighed to the above composition ratio, pulverized and mixed with ZrO 2 balls, and this mixed powder was calcined at 650-850 ° C. It is pulverized and mixed again with a ZrO 2 ball until the pulverized particle size becomes 2.5 μm or less, and this calcined powder is molded into a predetermined shape by a known method such as press molding or a doctor blade method, It can be obtained by baking at 920 ° C. or lower, particularly 870 to 920 ° C. for 0.5 to 2 hours in a non-oxidizing atmosphere such as a nitrogen atmosphere. The raw material powder may be a metal salt such as a hydroxide, carbonate, nitrate, etc. that generates an oxide upon firing.
[0036]
The alkaline earth metal is preferably added as a glass frit containing B, Li, and Si from the viewpoint of improving the sinterability. In this case, the amounts of B, Li, and Si are the total amount of the amount contained in the glass frit and the amount added as a powder.
[0037]
In the dielectric ceramic for high frequency of the present invention, Zr, Al, etc. may be mixed in the manufacturing process such as the mixing and pulverizing process of raw materials, or Al, Fe, Hf, Sn, etc. may be included as inevitable impurities of the raw materials. .
[0038]
In the high frequency dielectric ceramic according to the present invention, for example, MgTiO 3 and CaTiO 3 may be main crystal phases as crystal phases, and (Mg, Ti) 2 (BO 3 ) O may be precipitated. The alkaline earth metal is dissolved in the A site of MgTiO 3 and CaTiO 3 or becomes a glass component to improve the sinterability. Si exists as a glass phase. Furthermore, the high frequency dielectric ceramic of the present invention has an average crystal grain size of 1 to 5 μm.
[0039]
【Example】
Example 1
The purity of 99% as a raw material, MgO, CaO, SrO, and BaO powder used as B 2 O 3, Li 2 CO 3, SiO 2 powder, further alkaline earth oxides, weighed such that the ratio shown in Table 1 And a low loss ceramic filler component represented by a molar ratio of 0.95 MgTiO 3 .0.05CaTiO 3 (Qf value 100000) or BaO · 4.0TiO 2 (Qf value 50000), and ZrO 2 balls Wet mixing was performed for 20 hours in a ball mill using The mixture was then dried (dehydrated) and calcined at 800 ° C. for 1 hour. This calcined product was pulverized so that the pulverized particle size was 1.0 μm or less, and was press-molded at a pressure of 1 ton / cm 2 into a cylindrical shape having a diameter of 10 mm and a height of 8 mm as a sample for dielectric property evaluation. The sample was fired for 2 hours at the temperature shown in 1 to obtain a cylindrical sample having a diameter of 8 mm and a height of 6 mm. At this time, the shrinkage start temperature was measured by measuring heat shrinkage.
[0040]
Evaluation of dielectric characteristics was performed by measuring the relative dielectric constant and Q value at a frequency of 8 GHz by the dielectric cylindrical resonator method using the sample. Table 1 shows the Qf value represented by the product of the Q value and the measurement frequency f. Furthermore, the temperature coefficient τf [ppm / ° C.] of the resonance frequency in the temperature range of −40 to + 85 ° C. was measured. The results are shown in Table 1.
[0041]
[Table 1]
From Table 1, the dielectric ceramic according to the present invention has excellent dielectric characteristics with a relative dielectric constant of 18 to 40, a Qf value of 20000 [GHz] or more, and a temperature coefficient τf of resonance frequency within ± 40 ppm / ° C. It can be seen that sintering shrinkage starts at 760 to 830 ° C. and has excellent sinterability capable of firing at 920 ° C. or lower.
[0043]
As the alkali metal, Na was used for sample No. 4, K was used for No. 8, and Li was used for the others. As alkaline earth metals, sample No. 10 uses Ca, No. 11 uses Mg, No. 12 uses Ba, No. 13 uses Sr, and others use Ba and Ca. At this time, the weight ratio of BaO and CaO was 1: 1. Sample No. Reference numeral 13 is a reference sample.
[0044]
Example 2
MgTiO 3 powder, CaTiO 3 powder, B 2 O 3 powder, alkali metal carbonate powder (Li 2 CO 3 , Na 2 CO 3 , K 2 CO 3 ), SiO 2 powder, MnO 2 with a purity of 99% or more as a raw material Powder, and alkaline earth oxide powder (MgO, CaO, SrO, BaO) were weighed so as to have the ratio shown in Table 2, and wet for 20 hours in a ball mill using pure water as a medium and ZrO 2 balls. Mixed. The mixture was then dried (dehydrated) and calcined at 800 ° C. for 1 hour.
[0045]
This calcined product was pulverized so that the pulverized particle size was 1.0 μm or less, and was press-molded at a pressure of 1 ton / cm 2 into a cylindrical shape having a diameter of 10 mm and a height of 8 mm as a sample for dielectric property evaluation. The sample was baked at the temperature shown in 3 for 3 hours to obtain a cylindrical sample having a diameter of 8 mm and a height of 6 mm.
[0046]
Evaluation of dielectric characteristics was performed by measuring the relative dielectric constant and Q value at a frequency of 8 GHz by the dielectric cylindrical resonator method using the sample. Table 3 shows the Qf value expressed by the product of the Q value and the measurement frequency f. Furthermore, the temperature coefficient τf [ppm / ° C.] of the resonance frequency in the temperature range of −40 to + 85 ° C. was measured. The results are shown in Table 3. Sample No. Reference numeral 32 is a reference sample.
[0047]
[Table 2]
[Table 3]
From Tables 2 and 3, the dielectric ceramic composition of the present invention has a relative dielectric constant of 18 to 20, a Qf value of 20000 [GHz] or more, and a temperature coefficient τf of resonance frequency within ± 40 ppm / ° C. It can be seen that it has excellent dielectric properties, has sintering shrinkage at 760 to 830 ° C., and has excellent sinterability capable of firing at 920 ° C. or lower.
[0050]
In the alkali column of Table 1, Li, Na, and K are described. This means Li 2 CO 3 , Na 2 CO 3 , and K 2 CO 3 , and in the alkaline earth column, Although described as Mg, Ba, Ca, Sr, this means MgO, CaO, SrO, BaO. Furthermore, sample No. For 24 and 25, raw material powders with Mg / Ti and Ca / Ti ratios of 1.1 and 0.9, respectively, were used.
[0051]
【The invention's effect】
According to the present invention, since the firing temperature can be set to 920 ° C. or less and the shrinkage start temperature can be set to 830 ° C. or less, it can be fired simultaneously with a conductor metal such as Ag or Cu. The warpage and distortion of the substrate caused by the mismatch are suppressed, and since the Qf value is 20000 or more in the high frequency region, the electronic component and the substrate can be reduced in size and performance.
Claims (4)
ａＢ ２ Ｏ ３ ・ｂＡ ２ Ｏ・ｃＳｉＯ ２ ・ｄＲＯ
と表した時、前記ａ、ｂ、ｃおよびｄが、
４０≦ａ≦９０
８≦ｂ≦２０
１≦ｃ≦２０
１≦ｄ≦２０
ａ＋ｂ＋ｃ＋ｄ＝１００
Ａはアルカリ金属のうち少なくとも一種
Ｒはアルカリ土類金属としてＢｅ、Ｍｇ、ＣａおよびＢａのうち少なくとも一種
を満足することを特徴とする高周波用誘電体磁器。Grain boundary containing at least one of Be, Mg, Ca, and Ba as B, alkali metal, Si, and alkaline earth metal with respect to 100 parts by weight of low loss ceramic filler and 100 parts by weight of low loss ceramic filler A composition comprising 5 to 30 parts by weight of a phase forming component is fired, a Qf value represented by a product of a Q value and a measurement frequency thereof is 20000 [GHz] or more, and the grain boundary phase forming component is , Composition formula by weight ratio,
aB 2 O 3 · bA 2 O · cSiO 2 · dRO
Where a, b, c and d are
40 ≦ a ≦ 90
8 ≦ b ≦ 20
1 ≦ c ≦ 20
1 ≦ d ≦ 20
a + b + c + d = 100
A is at least one of alkali metals
R is at least one of Be, Mg, Ca and Ba as an alkaline earth metal
High frequency dielectric porcelain characterized by satisfying
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