JP3754827B2 - High frequency dielectric ceramic 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、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組成物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組成物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、誘電体磁器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、誘電体磁器と内部導体を同時焼成するに際しては、従来の誘電体磁器の焼成温度が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磁器が提案されている。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、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】
また、特開平９−３１５８５９号公報に開示された誘電体磁器組成物はＣａＯ、ＺｒＯ2 とＢ2 Ｏ3 、アルカリ金属化合物からなり、１２００℃以下の比較的低温で焼成できるものであった。
【０００６】
【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。また、特開平９−３１５８５９号公報に開示された誘電体磁器組成物も同様の問題があった。
【０００７】
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。
【０００８】
本発明は、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組成物および積層体を提供することを目的とする。
【０００９】
【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組成物は、金属元素としてＣａ、Ｚｒからなる複合酸化物であって、これらのモル比による組成式をｘＣａＯ・ＺｒＯ２と表した時、前記ｘが０．８７≦ｘ≦１．３６を満足する主成分と、該主成分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重量部とからなるとともに、該粒界相形成成分は、重量比による組成式を、
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のうち少なくとも一種を満足するものである。Ｑ値とその測定周波数でとの積で表されるＱｆ値は２００００［ＧＨｚ］以上であることが望ましい。
【００１１】
本発明の積層体は、誘電体層を複数積層してなる基体の内部および／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組成物からなるものである。
【００１２】
【作用】
本発明の高周波用誘電体磁器組成物は、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ｘＣａＯ・ＺｒＯ2 自体のＱｆ値をそれほど低下させることなく、９４０℃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１５０００〔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。
【００１３】
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、特には８００℃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。
【００１４】
本発明の積層体では、上記したような誘電体磁器組成物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、積層体の反り、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。
【００１５】
【発明の実施の形態】
本発明の高周波用誘電体磁器組成物は、金属元素としてＣａ、Ｚｒからなる複合酸化物であって、これらのモル比による組成式を、ｘＣａＯ・ＺｒＯ２と表した時、前記ｘが０．８７≦ｘ≦１．３６を満足する主成分と、該主成分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重量部とからなるものである。
【００１６】
ここで、上記組成式において、０．８７≦ｘ≦１．３６としたのは、ｘが０．８７未満の場合にはＱｆ値が低下し、ｘが１．３６を越える場合にはＱｆ値と焼結性が低下するからである。高いＱｆ値を得るという観点から０．９５≦ｘ≦１．２８が望ましい。
【００１７】
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９４０℃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、Ｑｆ値を１５０００〔ＧＨｚ〕以上とすることができるからである。
【００１８】
粒界相形成成分量を、主成分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、Ｑｆ値が低下してしまう。上記理由から、粒界相形成成分量は、主成分１００重量部に対して１０〜２０重量部が望ましい。
【００１９】
粒界相形成成分としては、重量比による組成式をａＢ２Ｏ３・ｂＡ２Ｏ・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を満足するものである。
【００２０】
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困難になり、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Ｑｆ値が低下するからである。よって、焼結性を維持し、高いＱｆ値を得るという観点から５０≦ａ≦７０重量％が望ましい。
【００２１】
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困難になり、逆に２０重量％を越える場合には、結晶相が変化してＱｆ値が低下したり、焼成温度が高くなるからである。誘電体磁器のＱｆ値の観点から１２≦ｂ≦２０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。
【００２２】
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Ｑｆ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Ｑｆ値の観点からは、ｃは５≦ｃ≦１５重量％が望ましい。
【００２３】
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比誘電率εｒあるいはＱｆ値が低下するからである。とりわけ誘電体磁器の焼結性とＱｆ値の観点からは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。
【００２４】
本発明の高周波用誘電体磁器は、原料粉末として、ＣａＣＯ3 粉末、ＺｒＯ2 粉末を所定量秤量し、該原料粉末をＺｒＯ2 等のボールにより混合・粉砕した後、該混合物を乾燥し、次いで該乾燥物を大気中等の酸化性雰囲気において１１００〜１４００℃の温度で１〜４時間仮焼する。
【００２５】
得られた仮焼粉に、例えばＢ2 Ｏ3 粉末、Ｌｉ2 ＣＯ3 粉末、ＳｉＯ2 粉末、さらにアルカリ土類金属含有化合物（炭酸塩、水酸化物等）粉末を所定量秤量添加し、ＺｒＯ2 ボールにより混合・粉砕し、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、乾燥して得た粉末を、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９４０℃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。
【００２６】
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。
【００２７】
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、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。
【００２８】
【実施例】
先ず、純度９９％以上のＣａＣＯ3 、ＺｒＯ2 の各原料粉末を表１に示す割合で秤量し、該原料粉末に媒体として純水を加えてＺｒＯ2 ボールを用いたボールミルにて２０時間粉砕・混合した後、該混合物を乾燥し、次いで乾燥物を大気中で１２００℃の温度で２時間仮焼した。
【００２９】
得られた仮焼物と純度９９％以上の、Ｂ2 Ｏ3 、Ｌｉ2 ＣＯ3 、Ｎａ2 ＣＯ3 、Ｋ2 ＣＯ3 、ＳｉＯ2 粉末、さらにアルカリ土類金属含有化合物として炭酸塩粉末を用い、表１に示す割合となるように秤量添加し、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し、８００℃で１時間仮焼した。
【００３０】
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約１０ｍｍ高さ約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、直径約８ｍｍ、高さ約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。
【００３１】
誘電特性の評価は、前記円柱試料の両端面を平面研削した後、誘電体円柱共振器法にて周波数８〜１０ＧＨｚ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。
【００３２】
尚、共振周波数の温度係数τｆは、２５℃での共振周波数を基準にして−４０℃および＋８５℃における共振周波数の温度係数τｆを算出した結果、すべての試料の共振周波数の温度係数τｆが±４０〔ｐｐｍ／℃〕の範囲内であった。尚、試料Ｎｏ．１４、１６、１８、１９、２０は参考試料である。
【００３３】
【表１】
この表１から、本発明の誘電体磁器組成物は、比誘電率が１８〜２９、Ｑｆ値が１５０００〔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、７７０〜８３０℃で焼結収縮が開始し、９４０℃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。
【００３５】
特に、粒界相形成成分が、上記組成範囲を満足する場合には、比誘電率が２２〜２９、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、７７０〜８３０℃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。
【００３６】
尚、アルカリ金属Ａとしては、試料Ｎo.６でＫを、Ｎo.２２でＮａを用い、その他はＬｉを用いた。また、アルカリ土類金属Ｒとしては、試料Ｎo.２でＭｇを、Ｎo.８でＢａを、Ｎo.１１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。
【００３７】
また、ＳｉＯ2 およびアルカリ土類金属を含有していない試料Ｎｏ．２５は、焼結開始温度は８５０℃と高温であることが判る。
【００３８】
【発明の効果】
本発明によれば、焼成温度を９４０℃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１５０００〔ＧＨｚ〕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 dielectric ceramic composition for high frequency and a laminate having a high Q value in a high frequency region such as microwaves and millimeter waves, and is used in, for example, a high frequency region such as microwaves and millimeter waves. The present invention relates to high-frequency dielectric ceramic compositions and laminates that can be used for various 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 popularization 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 electronic circuit boards and electronic components, when firing dielectric ceramics and internal conductors at the same time, 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 high conduction resistance, the conventional electronic circuit board has a problem that the Q value of the resonance circuit 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 or the like 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]
Moreover, the dielectric ceramic composition disclosed in Japanese Patent Application Laid-Open No. 9-315859 is made of CaO, ZrO 2 and B 2 O 3 , and an alkali metal compound, and can be fired at a relatively low temperature of 1200 ° C. or lower.
[0006]
[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. The dielectric ceramic composition disclosed in JP-A-9-315859 also has the same problem.
[0007]
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.
[0008]
The present invention can reduce the shrinkage start temperature to approach the shrinkage start temperature of the conductor, and can suppress warpage and distortion even when co-fired with a conductor mainly composed of Ag or Cu. It aims at providing a thing and a layered product.
[0009]
[Means for Solving the Problems]
The dielectric ceramic composition for high frequency of the present invention is a composite oxide composed of Ca and Zr as metal elements, and when the composition formula by these molar ratios is expressed as xCaO · ZrO 2 , the x is 0.87. ≦ x ≦ 1.36 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 main component, and 5 to 30 parts by weight In addition, the grain boundary phase forming component has a 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 satisfies at least one of the alkaline earth metals . The Qf value represented by the product of the Q value and its measurement frequency is preferably 20000 [GHz] or more.
[0011]
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 substrate formed by laminating a plurality of dielectric layers, wherein the dielectric layer is the above It consists of a high frequency dielectric ceramic composition.
[0012]
[Action]
The dielectric ceramic composition for high frequency of the present invention reduces the Qf value of the low-loss ceramic filler xCaO · ZrO 2 itself by the grain boundary phase forming component containing B, alkali metal, Si and alkaline earth metal. In addition, it can be fired at a firing temperature of 940 ° C. or lower, the shrinkage start temperature can be 830 ° C. or lower, and is not deformed even when simultaneously fired with an internal conductor such as Ag, Cu, and the Q value and its measurement frequency The Qf value of the porcelain expressed by the product of 1 is 15000 [GHz] or more, and it is suitably used for resonator materials, MIC dielectric substrate materials, dielectric waveguide materials, dielectric layers of multilayer ceramic capacitors, etc. be able to.
[0013]
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, In addition to firing at the firing temperature, the firing shrinkage start temperature can be made 830 ° C. or lower, particularly 800 ° C. or lower, and can approach the shrinkage start temperature of a conductor mainly composed of Ag and / or Cu. Even when co-fired with a conductor containing Cu as a main component, it is possible to suppress the occurrence of warping, distortion, etc. of the substrate and electronic parts, and the temperature coefficient τf of the resonance frequency is in the range of ± 40 ppm / ° C. Can It becomes a function.
[0014]
In the laminate of the present invention, by using the dielectric ceramic composition as described above, even when simultaneously fired with a conductor mainly composed of Ag and Cu, it is possible to suppress the occurrence of warpage, distortion, etc. of the laminate, In high frequency regions such as microwaves and millimeter waves, it can be suitably used for resonators, MIC substrates, and waveguides.
[0015]
DETAILED DESCRIPTION OF THE INVENTION
The high-frequency dielectric ceramic composition of the present invention is a composite oxide composed of Ca and Zr as metal elements. When the composition formula based on these molar ratios is expressed as xCaO · ZrO 2 , the x is 0.00. A main component satisfying 87 ≦ x ≦ 1.36, and 5 to 30 parts by weight of a grain boundary phase forming component containing B, alkali metal, Si and alkaline earth metal with respect to 100 parts by weight of the main component It will be.
[0016]
Here, in the above composition formula, 0.87 ≦ x ≦ 1.36 is set because the Qf value decreases when x is less than 0.87, and the Qf value when x exceeds 1.36. This is because the sinterability decreases. From the viewpoint of obtaining a high Qf value, 0.95 ≦ x ≦ 1.28 is desirable.
[0017]
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 940 ° C. or lower and the firing shrinkage start temperature This is because the Qf value can be 15000 [GHz] or more.
[0018]
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 main component. When the amount is less than 5 parts by weight, the effect of lowering the firing temperature is small, and Ag or Cu is the main component. When it exceeds 30 parts by weight, the Qf value decreases. For the above reasons, the grain boundary phase forming component amount is desirably 10 to 20 parts by weight with respect to 100 parts by weight of the main component.
[0019]
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 satisfy 40 ≦ a ≦ 90, 8 ≦ b ≦ 20, 1 ≦ c ≦ 20, 1 ≦ d ≦ 20, and a + b + c + d = 100 .
[0020]
Here, the B 2 O 3 amount a 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, if it exceeds 90% by weight, the ratio of the glass phase in the sintered body increases and the Qf value decreases. Therefore, 50 ≦ a ≦ 70 wt% is desirable from the viewpoint of maintaining sinterability and obtaining a high Qf value.
[0021]
Further, 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 simultaneous firing becomes difficult and, on the contrary, when the content exceeds 20% by weight, the crystal phase changes to lower the Qf value or increase the firing temperature. From the viewpoint of the Qf value of the dielectric ceramic, 12 ≦ b ≦ 20% 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.
[0022]
Furthermore, the SiO 2 amount c is set to 1 ≦ c ≦ 20% by weight. When c is less than 1% by weight, the shrinkage start temperature in the sintering process of the dielectric ceramic becomes high and the effect of addition cannot be obtained. Because. On the other hand, if the content exceeds 20% by weight, the dielectric constant εr or Qf value of the dielectric ceramic decreases. From the viewpoint of the dielectric constant εr or Qf value of the dielectric ceramic, c is preferably 5 ≦ c ≦ 15% by weight.
[0023]
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 high and the effect of addition cannot be obtained. . On the other hand, if the content exceeds 20% by weight, the dielectric constant εr or Qf value of the dielectric ceramic decreases. In particular, from the viewpoint of the sinterability of the dielectric ceramic and the Qf value, 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.
[0024]
In the dielectric ceramic for high frequency of the present invention, a predetermined amount of CaCO 3 powder and ZrO 2 powder are weighed as raw material powder, the raw material powder is mixed and pulverized with balls such as ZrO 2 , the mixture is then dried, The dried product is calcined at a temperature of 1100 to 1400 ° C. for 1 to 4 hours in an oxidizing atmosphere such as air.
[0025]
To the obtained calcined powder, for example, a predetermined amount of B 2 O 3 powder, Li 2 CO 3 powder, SiO 2 powder, and alkaline earth metal-containing compound (carbonate, hydroxide, etc.) powder is weighed and added. After mixing and pulverizing with two balls, this mixed powder was calcined at 650 to 850 ° C., and then again pulverized and dried with a ZrO 2 ball until the pulverized particle size became 2.5 μm or less. Formed into a predetermined shape by a known method such as a doctor blade method or the like, and fired at 940 ° C. or less, particularly at 870 to 920 ° C. for 0.5 to 2 hours in a non-oxidizing atmosphere such as air, oxygen atmosphere or nitrogen atmosphere Can be obtained. The raw material powder may be a metal salt such as a hydroxide, carbonate, nitrate, etc. that generates an oxide upon firing.
[0026]
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.
[0027]
In the dielectric ceramic for high frequency of the present invention, Al or the like may be mixed in a manufacturing process such as a raw material mixing and pulverizing process, or Al, Fe, Hf, Sn, or the like may be included as an inevitable impurity of the raw material.
[0028]
【Example】
First, each raw material powder of CaCO 3 and ZrO 2 having a purity of 99% or more is weighed in the proportions shown in Table 1, and pure water is added to the raw material powder as a medium, followed by grinding for 20 hours in a ball mill using ZrO 2 balls. After mixing, the mixture was dried and then the dried product was calcined in the atmosphere at a temperature of 1200 ° C. for 2 hours.
[0029]
The resulting calcined product with a purity of 99% or more, B 2 O 3, Li 2 CO 3, Na 2 CO 3, K 2 CO 3, SiO 2 powder, further using a carbonate powder as the alkaline earth metal-containing compound, Weighed and added so that the ratio shown in Table 1 was achieved, and wet-mixed for 20 hours in a ball mill using ZrO 2 balls using pure water as a medium. The mixture was then dried and calcined at 800 ° C. for 1 hour.
[0030]
This calcined product is pulverized so that the pulverized particle size is 1.0 μm or less, and is press-molded at a pressure of 1 ton / cm 2 into a cylindrical shape having a diameter of about 10 mm and a height of about 8 mm as a sample for dielectric property evaluation. Were fired at the temperature shown in Table 1 for 2 hours to obtain a cylindrical sample having a diameter of about 8 mm and a height of about 6 mm. At this time, the shrinkage start temperature was measured by measuring heat shrinkage.
[0031]
The dielectric properties were evaluated by measuring the relative dielectric constant and the Q value at a frequency of 8 to 10 GHz using a dielectric cylindrical resonator method after surface grinding of both end faces of the cylindrical sample. Table 1 shows the Qf value represented by the product of the Q value and the measurement frequency f.
[0032]
The temperature coefficient τf of the resonance frequency is calculated by calculating the temperature coefficient τf of the resonance frequency at −40 ° C. and + 85 ° C. with reference to the resonance frequency at 25 ° C. As a result, the temperature coefficient τf of the resonance frequency of all the samples is ± It was within the range of 40 [ppm / ° C.]. Sample No. Reference numerals 14, 16, 18, 19, and 20 are reference samples.
[0033]
[Table 1]
From Table 1, the dielectric ceramic composition of the present invention has an excellent dielectric constant with a relative dielectric constant of 18 to 29, a Qf value of 15000 [GHz] or more, and a temperature coefficient τf of resonance frequency within ± 40 ppm / ° C. It can be seen that it has properties and has excellent sinterability which starts sintering shrinkage at 770-830 ° C. and can be fired at 940 ° C. or less.
[0035]
In particular, when the grain boundary phase forming component satisfies the above composition range, the relative dielectric constant is 22 to 29, the Qf value is 20000 [GHz] or more, and the temperature coefficient τf of the resonance frequency is within ± 40 ppm / ° C. It can be seen that it has excellent dielectric properties, and sintering shrinkage starts at 770 to 830 ° C., and has excellent sinterability capable of firing at 920 ° C. or lower.
[0036]
As the alkali metal A, K was used for sample No. 6, Na was used for No. 22, and Li was used for the others. As the alkaline earth metal R, Mg was used in sample No. 2, Ba was used in No. 8, Sr was used in No. 11, and Ba and Ca were used in the other cases. At this time, the weight ratio of BaO and CaO was 1: 1.
[0037]
Sample No. 2 containing no SiO 2 or alkaline earth metal was used. No. 25 shows that the sintering start temperature is as high as 850 ° C.
[0038]
【The invention's effect】
According to the present invention, since the firing temperature can be set to 940 ° 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 the Qf value is 15000 [GHz] or higher in the high frequency region, so that the electronic components and the substrate can be reduced in size and performance.
Claims (2)
ｘＣａＯ・ＺｒＯ２
と表した時、前記ｘが
０．８７≦ｘ≦１．３６
を満足する主成分と、該主成分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重量部とからなるとともに、該粒界相形成成分は、重量比による組成式を、
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組成物。It is a complex oxide composed of Ca and Zr as metal elements, and the composition formula by these molar ratios is expressed as xCaO · ZrO 2
Where x is 0.87 ≦ x ≦ 1.36.
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 main component, and the grain boundary phase The forming component has a 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 a dielectric ceramic composition for high frequency, wherein R satisfies at least one of alkaline earth metals .
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|---|---|---|---|
| JP27689898A JP3754827B2 (en) | 1998-09-30 | 1998-09-30 | High frequency dielectric ceramic composition and laminate |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27689898A JP3754827B2 (en) | 1998-09-30 | 1998-09-30 | High frequency dielectric ceramic composition and laminate |
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| Publication Number | Publication Date |
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