JP3860687B2 - Dielectric porcelain 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値を有する誘電体磁器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磁器やＭＩＣ用誘電体基板、誘電体導波路や積層型セラミックコンデンサ等に用いることができる誘電体磁器および積層体に関するものである。
【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】
また、上記公報に開示された誘電体磁器組成物では、比誘電率εｒが１８以上と高いため、この誘電体磁器組成物を用いて高周波用のモジュール基板を作製すると、例えば、容量を必要としない配線間、線路間、配線と線路間等に浮遊容量（寄生容量）が発生し、高周波特性が劣化したり、回路上の制約が生じるという問題があった。
【０００８】
本発明は上記課題に鑑みなされたもので、焼成温度を従来よりもさらに低下させることができ、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とともに、比誘電率の低い誘電体磁器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】
本発明の誘電体磁器は、フォルステライト結晶粒子と（Ｍｇ，Ｔｉ） ２ （ＢＯ ３ ）Ｏからなる結晶粒子とを含むとともに、粒界に、元素としてＢ、Ｌｉ、アルカリ土類金属が存在するものである。
【００１０】
このような構成を採用することにより、フォルステライト本来のＱ値をそれほど劣化させることなく、９２０℃以下の低温焼成が可能となるとともに、フォルステライト自体が低誘電率であるため、比誘電率を大きく低下できる。
【００１１】
ここで、誘電体磁器は、ＭｇをＭｇＯ換算で２８．８〜４２．０重量％、ＴｉをＴｉＯ ２ 換算で１２．４〜４８．０重量％、ＢをＢ ２ Ｏ ３ 換算で８．９〜１５．３重量％含有することが望ましい。また、誘電体磁器は、ＬｉをＬｉ ２ ＣＯ ３ 換算で０．８〜８．０重量％、アルカリ土類金属を酸化物換算で０．８〜４．６重量％、ＳｉをＳｉＯ ２ 換算で３．４〜３８．７重量％含有することが望ましい。
【００１２】
このような構成を採用することにより、比誘電率が６〜１２で、測定周波数１０ＧＨｚでのＱ値が１０００以上であり、かつ、焼成温度を８７０〜９２０℃、収縮開始温度を７６０〜８６０℃とすることが可能となる。従って、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反りや歪み等の発生を抑制することができる。
【００１３】
また、ＭｎをＭｎＯ ２ 換算で０．９〜２．２重量％含有することが望ましい。これにより、誘電体磁器の焼結性をさらに向上できる。
【００１４】
本発明の積層体は、誘電体層を複数積層してなる誘電基板の内部および／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、前記誘電体層のうち少なくとも一層が上記誘電体磁器からなるものである。
【００１５】
このような構成を採用することにより、内部導体としてＡｇおよび／またはＣｕを主成分とする導体を使用しても積層体の変形がなく、高い高周波特性を有するとともに、低温焼成ができ、さらに、誘電体層が低誘電率であるため、容量を必要としない配線間、線路間、配線と線路間等における浮遊容量の発生を抑制できる。
【００１６】
【発明の実施の形態】
本発明の誘電体磁器は、フォルステライト結晶粒子と（Ｍｇ，Ｔｉ） ２ （ＢＯ ３ ）Ｏからなる結晶粒子とを含むとともに、粒界に、元素としてＢ、Ｌｉ、アルカリ土類金属が存在するものである。
【００１７】
そして、モル比による組成式を（１−ｘ）Ｍｇ２ＳｉＯ４・ｘＭｇＴｉＯ３と表した時、ｘが、０≦ｘ≦０．８を満足する主成分と、該主成分１００重量部に対して、ＢをＢ２Ｏ３換算で３〜２０重量部、ＬｉをＬｉ２ＣＯ３換算で１〜１０重量部、ＳｉをＳｉＯ２換算で０〜３０重量部、アルカリ土類金属を酸化物換算で１〜５重量部含有することが望ましい。
【００１８】
ここで、Ｍｇ2 ＳｉＯ4 とＭｇＴｉＯ3 のモル比ｘを、０≦ｘ≦０．８としたのは、ｘが０．８を越える場合には、高誘電率のＭｇＴｉＯ3 の割合が増加するため、比誘電率が大きくなるからである。とりわけ誘電体磁器の比誘電率を小さくするという点からｘは０≦ｘ≦０．５が好ましい。さらに、例えば、本発明の誘電体層とＭｇＴｉＯ3 −ＣａＴｉＯ3 系の誘電体層との積層体を作製する場合には、焼成収縮挙動を近くするという点からｘは０＜ｘ≦０．５が望ましい。
【００１９】
また、主成分１００重量部に対して、Ｂ ２Ｏ３換算量が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ＢはＢ２Ｏ３換算で５〜１５重量部含有することが望ましい。また、誘電体磁器の全量中にＢをＢ ２ Ｏ ３ 換算で８．９〜１５．３重量％含有することが望ましい。硼素含有化合物としては、金属硼素、Ｂ２Ｏ３、コレマイト、ＣａＢ２Ｏ４、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。また、誘電体磁器の全量中にＭｇをＭｇＯ換算で２８．８〜４２．０重量％、ＴｉをＴｉＯ ２ 換算で１２．４〜４８．０重量％含有することが望ましい。
【００２０】
また、Ｌｉ２ＣＯ３換算量が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、Ｑ値が低下するからである。焼結性と誘電体磁器のＱ値の観点からＬｉのＬｉ２ＣＯ３換算量は４〜９重量部が望ましい。また、誘電体磁器の全量中にＬｉをＬｉ ２ ＣＯ ３ 換算で０．８〜８．０重量％含有することが望ましい。
【００２１】
さらに、ＳｉＯ２換算量が３０重量部を越えると、ガラス相の割合が減少してＱ値が低下するからである。誘電体磁器のＱ値の観点からは、ＳｉのＳｉＯ２換算量は１０重量部以下含有することが望ましい。また、また、誘電体磁器の全量中にＳｉをＳｉＯ ２ 換算で３．４〜３８．７重量％含有することが望ましい。
【００２２】
また、主成分１００重量部に対して、アルカリ土類金属（Ｍｇ、Ｃａ、Ｓｒ、Ｂａ）の少なくとも一種を酸化物換算で１〜５重量部含有したのは、これらが酸化物換算で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約８７０℃と高く、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Ｑ値が低下する。とりわけ誘電体磁器の焼結性とＱ値の観点からはアルカリ土類金属は酸化物（ＭｇＯ，ＣａＯ，ＳｒＯ，ＢａＯ）換算で合計１．５〜３．５重量部含有することが好ましい。アルカリ土類金属はＢａ、Ｃａが高Ｑ値となるという点から望ましい。また、誘電体磁器の全量中にアルカリ土類金属を酸化物換算で０．８〜４．６重量％含有することが望ましい。
【００２３】
さらに、本発明の誘電体磁器では、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小さく、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。また、誘電体磁器の全量中にＭｎをＭｎＯ ２ 換算で０．９〜２．２重量％含有することが望ましい。
【００２４】
本発明の誘電体磁器は、原料粉末として、例えば、Ｍｇ2 ＳｉＯ4 粉末と、ＭｇＴｉＯ3 粉末と、Ｂ2 Ｏ3 粉末、Ｌｉ2 ＣＯ3 粉末、ＳｉＯ2 粉末、アルカリ土類酸化物粉末（ＭｇＯ，ＣａＯ，ＳｒＯ，ＢａＯ）を準備し、これらを上記した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、混合する。
【００２５】
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、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。本発明の誘電体磁器中には、不可避不純物として、Ａｌ、Ｆｅ、Ｈｆ、Ｓｎ等が含まれることもある。
【００２６】
アルカリ土類金属は、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。例えば、Ｂ2 Ｏ3 粉末、Ｌｉ2 ＣＯ3 粉末、ＳｉＯ2 粉末、アルカリ土類金属酸化物粉末を用いてガラスフリットを作製して添加する。この際、Ｂ2 Ｏ3 粉末、Ｌｉ2 ＣＯ3 粉末、ＳｉＯ2 粉末、アルカリ土類酸化物粉末として添加される量は、上記ガラスフリットで用いられた量を差し引いた量であることは言うまでもない。
【００２７】
本発明の誘電体磁器では、フォルステライト結晶粒子を主結晶粒子とし、これに必要に応じて金属元素として少なくともＭｇとＴｉを含有する複合酸化物からなる結晶粒子、主には（Ｍｇ，Ｔｉ）2 （ＢＯ3 ）Ｏが析出し、組成によってはＭｇＴｉＯ3 が析出する場合もある。
【００２８】
尚、アルカリ土類金属は、ＭｇＴｉＯ3 のＡサイトに固溶したり、あるいはガラスとなって、焼結性を向上させることになる。本発明の誘電体磁器では平均結晶粒径が１〜５μｍのものである。
【００２９】
本発明の積層体は、誘電体層を複数積層してなる誘電基板の内部および／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、誘電体層のうち少なくとも一層が上記誘電体磁器からなるものであり、例えば、本発明の低誘電率の誘電体層と高誘電率のＭｇＴｉＯ3 −ＣａＴｉＯ3 系の誘電体層との積層体を作製すると、高誘電率が要求されるコンデンサ、フィルタ等を高誘電率のＭｇＴｉＯ3 −ＣａＴｉＯ3 系の誘電体層で形成し、配線間等の浮遊容量を発生させたくない配線等については、本発明の低誘電率の誘電体層で形成することができる。
【００３０】
このような積層体では、内部導体としてＡｇおよび／またはＣｕを主成分とする導体を使用しても積層体の変形がなく、高い高周波特性を有するとともに、低温焼成ができ、さらに、誘電体層のうち少なくとも一層が本発明の低誘電率の誘電体磁器からなるため、この誘電体層を利用して電極、線路等を形成することにより、容量を必要としない配線間、線路間、配線と線路間等における浮遊容量の発生を抑制できる。
【００３１】
【実施例】
Ｂ２Ｏ３粉末、Ｌｉ２ＣＯ３粉末、ＳｉＯ２粉末、アルカリ土類酸化物（ＭｇＯ，ＣａＯ，ＳｒＯ，ＢａＯ）粉末を表１に示すような組成で添加し、これを用いて作製されたガラスフリットと、原料として純度９９％以上のＭｇ２ＳｉＯ４、ＭｇＴｉＯ３粉末を表１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。なお、表１において括弧中にない値は、主成分を１００重量部として、この主成分１００重量部に対して加えた各成分を重量部で表示したものである。また、表１において括弧中に示した値は、誘電体磁器中に各成分が占める割合を重量％で示したものである。すなわち、まず、主成分を１００重量部とし、これにＢ ２ Ｏ ３ 、Ｌｉ ２ ＣＯ ３ 、ＳｉＯ ２ 、アルカリ土類酸化物の重量部を加えると１００重量部を超える値となる。この値で、各成分の重量部を除し、さらに１００を掛けると括弧中の重量％で表される値となる。
【００３２】
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１．４μｍ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０．０１ｍ、高さ０．００８ｍの円柱状に１００００ｔｏｎ／ｍ2 の圧力でプレス成形し、これを９００℃で２時間焼成し、直径０．００８ｍ、高さ０．００６ｍの円柱状の試料を得た。
【００３３】
尚、本発明者等は、Ｘ線回折測定およびＸ線マイクロアナライザー（ＥＰＭＡ）により、本発明の試料では主結晶粒子がフォルステライト結晶粒子と、（Ｍｇ，Ｔｉ）２（ＢＯ３）Ｏで表される結晶粒子が存在し、粒界に、元素としてＢ、Ｌｉ、アルカリ土類金属が存在することを確認した。
【００３４】
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１０ＧＨｚにおける比誘電率とＱ値を測定した。
【００３５】
【表１】
この表１から、本発明の誘電体磁器では、比誘電率が６〜１４、測定周波数１０ＧＨｚでのＱ値が５００以上の誘電特性を有するとともに、焼成温度を９２０℃以下とすることができ、焼成収縮開始温度を８６０℃以下とできる。
【００３７】
特に、モル比による組成式（１−ｘ）Ｍｇ2 ＳｉＯ4 ・ｘＭｇＴｉＯ3 においてｘが、０≦ｘ≦０．８を満足し、ＢをＢ2 Ｏ3 換算で３〜２０重量部、ＬｉをＬｉ2 ＣＯ3 換算で１〜１０重量部、ＳｉをＳｉＯ2 換算で０〜３０重量部、アルカリ土類金属を酸化物換算で１〜５重量部含有する場合には、比誘電率が６〜１２で、測定周波数１０ＧＨｚでのＱ値が１０００以上であり、かつ、焼成温度を８７０〜９２０℃、収縮開始温度を７６０〜８６０℃とできることが判る。これにより、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反りや歪み等の発生を抑制することができる。
【００３８】
一方、Ｌｉを含有しない場合には、試料Ｎo.７に示すように、焼成温度が１１５０℃、収縮開始温度が１０５０℃と高くなり、Ａｇ、Ｃｕを主成分とする導体と同時焼成できないことが判る。
【００３９】
さらに、アルカリ土類金属を含有しない場合には、試料Ｎo.１１に示すように、焼成温度が９５０℃、収縮開始温度が８７０℃と高くなることが判る。
【００４０】
【発明の効果】
以上詳述した通り、本発明によれば、フォルステライト本来のＱ値をそれほど劣化させることなく、９２０℃以下の低温焼成が可能となるとともに、フォルステライト自体が低誘電率であるため、比誘電率を１４以下と低下できる。
【００４１】
特に、モル比による組成式を、（１−ｘ）Ｍｇ2 ＳｉＯ4 ・ｘＭｇＴｉＯ3 と表した時、ｘが、０≦ｘ≦０．８を満足する主成分と、該主成分１００重量部に対して、ＢをＢ2 Ｏ3 換算で３〜２０重量部、ＬｉをＬｉ2 ＣＯ3 換算で１〜１０重量部、ＳｉをＳｉＯ2 換算で０〜３０重量部、アルカリ土類金属を酸化物換算で１〜５重量部含有する誘電体磁器では、比誘電率が６〜１２で、測定周波数１０ＧＨｚでのＱ値が１０００以上であり、かつ、焼成温度を８７０〜９２０℃、収縮開始温度を７６０〜８６０℃とすることができ、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反りや歪み等の発生を抑制することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a dielectric ceramic having a high Q value in a high frequency region such as a microwave and a millimeter wave. For example, various resonator ceramics and MICs used in a high frequency region such as a microwave and a millimeter wave. The present invention relates to a dielectric ceramic that can be used for a dielectric substrate, a dielectric waveguide, a multilayer ceramic capacitor, and the like, and a multilayer body.
[0002]
[Prior art]
Conventionally, dielectric ceramics are widely used for dielectric resonators, dielectric substrates for MICs, waveguides, and the like in a high frequency region such as microwaves and millimeter waves. In recent years, with the development and widespread use 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 internal conductors such as Ag and Cu at a relatively low temperature of 900 to 1050 ° C., and has an excellent characteristic that the dielectric constant εr of the dielectric ceramic is 18 or more, and the Q value at a measurement frequency of 7 GHz is 2000 or more. Therefore, the high-frequency electronic components can be reduced in size and performance.
[0005]
[Problems to be solved by the invention]
However, the dielectric ceramic composition disclosed in Japanese Patent Application Laid-Open No. 8-208330 has a high sintering temperature and a shrinkage start temperature in sintering as high as 845 to 960 ° C. 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]
Moreover, since the dielectric ceramic composition disclosed in the above publication has a high relative dielectric constant εr of 18 or more, when a high-frequency module substrate is produced using this dielectric ceramic composition, for example, a capacitance is required. There is a problem in that stray capacitance (parasitic capacitance) is generated between wirings that are not connected, between lines, between wirings, and the like, so that high-frequency characteristics are deteriorated and restrictions on circuits are generated.
[0008]
The present invention has been made in view of the above problems, and can lower the firing temperature further than before, lower the shrinkage start temperature, and can approach the shrinkage start temperature of the conductor. An object of the present invention is to provide a dielectric ceramic and a laminate that can suppress warping and distortion even when fired simultaneously with a conductor as described above and have a low relative dielectric constant.
[0009]
[Means for Solving the Problems]
The dielectric ceramic of the present invention includes forsterite crystal particles and crystal particles made of (Mg, Ti) 2 (BO 3 ) O, and B, Li, and alkaline earth metal are present as elements at the grain boundaries. Is.
[0010]
By adopting such a configuration, low-temperature firing at 920 ° C. or less is possible without significantly degrading the original Q value of forsterite, and forsterite itself has a low dielectric constant. Can be greatly reduced.
[0011]
Here, in the dielectric ceramic, Mg is 28.8 to 42.0 wt% in terms of MgO, Ti is 12.4 to 48.0 wt% in terms of TiO 2 , and B is 8.9 in terms of B 2 O 3. It is desirable to contain -15.3 wt% . The dielectric porcelain, the Li from .8 to 8.0% by weight Li 2 CO 3 terms, from 0.8 to 4.6 wt% in terms of oxide of the alkaline earth metals, the Si in terms of SiO 2 It is desirable to contain 3.4 to 38.7% by weight.
[0012]
By adopting such a configuration, the relative dielectric constant is 6 to 12, the Q value at a measurement frequency of 10 GHz is 1000 or more, the firing temperature is 870 to 920 ° C., and the shrinkage start temperature is 760 to 860 ° C. It becomes possible. Therefore, even when a substrate or an electronic component is simultaneously fired with a conductor containing Ag and Cu as main components, the occurrence of warpage, distortion, and the like can be suppressed.
[0013]
Further, it is desirable to contain 0.9 to 2.2 wt% of Mn with MnO 2 basis. Thereby, the sinterability of the dielectric ceramic can be further improved.
[0014]
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, Of these, at least one layer is made of the dielectric ceramic.
[0015]
By adopting such a configuration, even when a conductor mainly composed of Ag and / or Cu is used as an internal conductor, the laminate is not deformed, has high-frequency characteristics, and can be fired at a low temperature. Since the dielectric layer has a low dielectric constant, it is possible to suppress the generation of stray capacitance between wires that do not require capacitance, between lines, between wires and lines, and the like.
[0016]
DETAILED DESCRIPTION OF THE INVENTION
The dielectric ceramic of the present invention includes forsterite crystal particles and crystal particles made of (Mg, Ti) 2 (BO 3 ) O, and B, Li, and alkaline earth metal are present as elements at the grain boundaries. Is.
[0017]
And when the composition formula by molar ratio is expressed as (1-x) Mg 2 SiO 4 .xMgTiO 3 , x is a main component satisfying 0 ≦ x ≦ 0.8 and 100 parts by weight of the main component B is 3 to 20 parts by weight in terms of B 2 O 3 , Li is 1 to 10 parts by weight in terms of Li 2 CO 3 , Si is 0 to 30 parts by weight in terms of SiO 2 , and alkaline earth metal is in terms of oxide It is desirable to contain 1-5 parts by weight .
[0018]
Here, the molar ratio x between Mg 2 SiO 4 and MgTiO 3 is set to 0 ≦ x ≦ 0.8. When x exceeds 0.8, the proportion of MgTiO 3 having a high dielectric constant increases. This is because the relative dielectric constant increases. In particular, x is preferably 0 ≦ x ≦ 0.5 from the viewpoint of reducing the dielectric constant of the dielectric ceramic. Further, for example, when a laminate of the dielectric layer of the present invention and a MgTiO 3 —CaTiO 3 based dielectric layer is produced, x is 0 <x ≦ 0.5 from the viewpoint of close firing shrinkage behavior. Is desirable.
[0019]
In addition, when the B 2 O 3 equivalent amount is less than 3 parts by weight with respect to 100 parts by weight of the main component, sintering is not performed even at 1100 ° C., and co-firing with a conductor having Ag or Cu as the main component becomes impossible. Conversely, when it 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 of B in terms of B 2 O 3 from the viewpoint of maintaining sinterability and obtaining a high Q value. Moreover, it is desirable to contain 8.9 to 15.3% by weight of B in terms of B 2 O 3 in the total amount of the dielectric ceramic . Examples of the boron-containing compound include metal boron, B 2 O 3 , collimite, CaB 2 O 4 , borosilicate glass, borosilicate alkali glass, and borosilicate alkaline earth glass. Further, it is desirable to contain 28.8 to 42.0% by weight of Mg in terms of MgO and 12.4 to 48.0% by weight of Ti in terms of TiO 2 in the total amount of the dielectric ceramic .
[0020]
In addition , when the Li 2 CO 3 equivalent is less than 1 part by weight, it does not sinter even at 1100 ° C., and cannot be co-fired with a conductor mainly composed of Ag or Cu, and conversely exceeds 10 parts by weight. This is because the Q value decreases. From the viewpoint of the sinterability and the Q value of the dielectric ceramic, the Li 2 CO 3 equivalent amount of Li is preferably 4 to 9 parts by weight. Further, it is desirable to contain Li in an amount of 0.8 to 8.0% by weight in terms of Li 2 CO 3 in the total amount of the dielectric ceramic .
[0021]
Furthermore , if the SiO 2 equivalent exceeds 30 parts by weight, the glass phase ratio decreases and the Q value decreases. From the viewpoint of the Q value of the dielectric ceramic, it is desirable that the amount of Si converted to SiO 2 is 10 parts by weight or less. Further, it is desirable that Si is contained in an amount of 3.4 to 38.7% by weight in terms of SiO 2 in the total amount of the dielectric ceramic .
[0022]
Moreover, the reason why 1 to 5 parts by weight of an alkaline earth metal (Mg, Ca, Sr, Ba) is contained in terms of oxide is 1 weight in terms of oxide with respect to 100 parts by weight of the main component. In the case of less than the part, the shrinkage start temperature in the sintering process of the dielectric ceramic is as high as about 870 ° C., and the addition effect cannot be obtained. On the other hand, when the amount exceeds 5 parts by weight, the Q value of the dielectric ceramic decreases. In particular, from the viewpoint of sinterability and Q value of the dielectric ceramic, the alkaline earth metal is preferably contained in a total amount of 1.5 to 3.5 parts by weight in terms of oxide (MgO, CaO, SrO, BaO). Alkaline earth metals are desirable because Ba and Ca have high Q values. Moreover, it is desirable to contain 0.8 to 4.6% by weight of an alkaline earth metal in terms of oxide in the total amount of the dielectric ceramic.
[0023]
Furthermore, in the 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 addition effect is small 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 . Further, it is desirable to contain 0.9 to 2.2% by weight of Mn in terms of MnO 2 in the total amount of the dielectric ceramic .
[0024]
The dielectric ceramic of the present invention includes, for example, Mg 2 SiO 4 powder, MgTiO 3 powder, B 2 O 3 powder, Li 2 CO 3 powder, SiO 2 powder, alkaline earth oxide powder (MgO) as raw material powder. , CaO, SrO, BaO) are prepared, weighed so as to have the above-described composition ratio, pulverized and mixed with a ZrO 2 ball, this mixed powder was calcined at 650 to 850 ° C., and then again ZrO 2 ball The mixture is pulverized and mixed until the pulverized particle size becomes 2.5 μm or less.
[0025]
This calcined powder is molded into a predetermined shape by a known method such as press molding or a doctor blade method, and is 0.5 to 2 hours at 870 to 920 ° C. in a non-oxidizing atmosphere such as air, oxygen atmosphere or nitrogen atmosphere. It is obtained by firing. The raw material powder may be a metal salt such as a hydroxide, carbonate, nitrate, etc. that generates an oxide upon firing. The dielectric ceramic of the present invention may contain Al, Fe, Hf, Sn, etc. as inevitable impurities.
[0026]
The alkaline earth metal is preferably added as a glass frit from the viewpoint of improving the sinterability. For example, a glass frit is prepared and added using B 2 O 3 powder, Li 2 CO 3 powder, SiO 2 powder, or alkaline earth metal oxide powder. At this time, it goes without saying that the amount added as B 2 O 3 powder, Li 2 CO 3 powder, SiO 2 powder, alkaline earth oxide powder is an amount obtained by subtracting the amount used in the glass frit. .
[0027]
In the dielectric ceramic according to the present invention, forsterite crystal particles are used as main crystal particles, and crystal particles made of a complex oxide containing at least Mg and Ti as metal elements as necessary, mainly (Mg, Ti). 2 (BO 3 ) O precipitates, and MgTiO 3 may precipitate depending on the composition.
[0028]
The alkaline earth metal is solid-solved at the A site of MgTiO 3 or becomes glass to improve the sinterability. The dielectric ceramic of the present invention has an average crystal grain size of 1 to 5 μm.
[0029]
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, At least one layer is made of the above dielectric ceramic. For example, when a laminate of the low dielectric constant dielectric layer of the present invention and a high dielectric constant MgTiO 3 —CaTiO 3 dielectric layer is produced, The low dielectric constant of the present invention is used for wiring, etc., in which capacitors, filters, etc. that require a high dielectric constant are formed of a high dielectric constant MgTiO 3 —CaTiO 3 based dielectric layer and the floating capacitance between wirings and the like is not to be generated. The dielectric layer can be formed.
[0030]
In such a laminated body, even when a conductor mainly composed of Ag and / or Cu is used as an internal conductor, the laminated body is not deformed, has high-frequency characteristics, and can be fired at a low temperature. Of these, at least one layer is made of the dielectric ceramic having a low dielectric constant according to the present invention, so that electrodes, lines, etc. are formed using this dielectric layer, so that no wiring is required between the lines, between the lines, Generation of stray capacitance between lines can be suppressed.
[0031]
【Example】
B 2 O 3 powder, Li 2 CO 3 powder, SiO 2 powder, alkaline earth oxide (MgO, CaO, SrO, BaO) powder was added in the composition shown in Table 1 and produced using this. Glass frit and Mg 2 SiO 4 and MgTiO 3 powders with a purity of 99% or more as raw materials are weighed so as to have the ratios shown in Table 1, and are wet for 20 hours in a ball mill using pure water as a medium and ZrO 2 balls. Mixed. In Table 1, values that are not in parentheses are those in which the main component is 100 parts by weight and each component added to 100 parts by weight of the main component is expressed in parts by weight. Further, the values shown in parentheses in Table 1 indicate the ratio of each component in the dielectric ceramic in weight%. That is, first, when the main component is 100 parts by weight, and the parts by weight of B 2 O 3 , Li 2 CO 3 , SiO 2 and alkaline earth oxide are added to this, the value exceeds 100 parts by weight. When this part is divided by the weight part of each component and multiplied by 100, the value is expressed in weight% in parentheses.
[0032]
The mixture was then dried (dehydrated) and calcined at 800 ° C. for 1 hour. The calcined product is pulverized so that the pulverized particle size is 1.4 μm or less, and is press-molded at a pressure of 10000 ton / m 2 into a cylindrical shape having a diameter of 0.01 m and a height of 0.008 m as a sample for dielectric property evaluation. This was fired at 900 ° C. for 2 hours to obtain a cylindrical sample having a diameter of 0.008 m and a height of 0.006 m.
[0033]
In addition, the present inventors, by X-ray diffraction measurement and X-ray microanalyzer (EPMA), in the sample of the present invention, the main crystal particles are represented by forsterite crystal particles and (Mg, Ti) 2 (BO 3 ) O. It was confirmed that crystal grains to be present exist, and B, Li, and alkaline earth metal exist as elements at the grain boundaries.
[0034]
Evaluation of dielectric characteristics was performed by measuring the relative dielectric constant and Q value at a frequency of 10 GHz by the dielectric cylindrical resonator method using the sample.
[0035]
[Table 1]
From Table 1, in the dielectric ceramic of the present invention, the dielectric constant is 6 to 14, the Q value at a measurement frequency of 10 GHz is 500 or more, and the firing temperature can be 920 ° C. or less. The firing shrinkage start temperature can be 860 ° C. or less.
[0037]
In particular, in the composition formula (1-x) Mg 2 SiO 4 .xMgTiO 3 by molar ratio, x satisfies 0 ≦ x ≦ 0.8, B is 3 to 20 parts by weight in terms of B 2 O 3 , and Li is When containing 1 to 10 parts by weight in terms of Li 2 CO 3 , 0 to 30 parts by weight in terms of Si 2 in terms of SiO 2 , and 1 to 5 parts by weight in terms of oxides of alkaline earth metals, the relative dielectric constant is 6 to 12 shows that the Q value at a measurement frequency of 10 GHz is 1000 or more, the firing temperature can be set to 870 to 920 ° C., and the shrinkage start temperature can be set to 760 to 860 ° C. Thereby, in a board | substrate and an electronic component, generation | occurrence | production of a curvature, a distortion | strain, etc. can be suppressed even when co-firing with the conductor which has Ag and Cu as a main component.
[0038]
On the other hand, when Li is not contained, as shown in Sample No. 7, the firing temperature is as high as 1150 ° C. and the shrinkage start temperature is as high as 1050 ° C., which cannot be simultaneously fired with a conductor mainly composed of Ag and Cu. I understand.
[0039]
Further, when no alkaline earth metal is contained, as shown in Sample No. 11, it can be seen that the firing temperature is as high as 950 ° C. and the shrinkage start temperature is as high as 870 ° C.
[0040]
【The invention's effect】
As described in detail above, according to the present invention, low-temperature firing at 920 ° C. or less is possible without significantly degrading the original Q value of forsterite, and the forsterite itself has a low dielectric constant. The rate can be reduced to 14 or less.
[0041]
In particular, when the composition formula by molar ratio is expressed as (1-x) Mg 2 SiO 4 .xMgTiO 3 , x is a main component satisfying 0 ≦ x ≦ 0.8, and 100 parts by weight of the main component. On the other hand, B is 3 to 20 parts by weight in terms of B 2 O 3 , Li is 1 to 10 parts by weight in terms of Li 2 CO 3 , Si is 0 to 30 parts by weight in terms of SiO 2 , and alkaline earth metal is an oxide In a dielectric ceramic containing 1 to 5 parts by weight in terms of relative dielectric constant, the dielectric constant is 6 to 12, the Q value at a measurement frequency of 10 GHz is 1000 or more, the firing temperature is 870 to 920 ° C., and the shrinkage start temperature is The temperature can be set to 760 to 860 ° C., and the occurrence of warpage, distortion, and the like can be suppressed even when the substrate and the electronic component are simultaneously fired with a conductor mainly composed of Ag and Cu.
Claims (5)
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30836399A JP3860687B2 (en) | 1999-10-29 | 1999-10-29 | Dielectric porcelain and laminate |
| EP00123551A EP1096674B1 (en) | 1999-10-29 | 2000-10-27 | Circuit substrate |
| US09/699,666 US6417461B1 (en) | 1999-10-29 | 2000-10-30 | Circuit substrate |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30836399A JP3860687B2 (en) | 1999-10-29 | 1999-10-29 | Dielectric porcelain and laminate |
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| JP2001130952A JP2001130952A (en) | 2001-05-15 |
| JP3860687B2 true JP3860687B2 (en) | 2006-12-20 |
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| JP4535592B2 (en) * | 2000-09-28 | 2010-09-01 | 京セラ株式会社 | Laminated body |
| JP4632534B2 (en) * | 2000-12-27 | 2011-02-16 | 京セラ株式会社 | Dielectric porcelain and manufacturing method thereof |
| JP5187997B2 (en) * | 2001-09-19 | 2013-04-24 | 京セラ株式会社 | Dielectric porcelain, method of manufacturing the same, and dielectric resonator using the same |
| WO2004106261A1 (en) * | 2003-05-30 | 2004-12-09 | Nagoya Industrial Science Research Institute | High-frequency porcelain composition, process for producing the same and planar high-frequency circuit |
| KR100567322B1 (en) * | 2003-12-12 | 2006-04-04 | 한국전자통신연구원 | Dielectric ceramic composition of forsterite system for microwave and millimeter-wave application and method for forming the same |
| JP5170522B2 (en) * | 2007-02-22 | 2013-03-27 | Ｔｄｋ株式会社 | Dielectric porcelain composition |
| EP2371787B1 (en) * | 2008-11-25 | 2013-03-06 | Ube Industries, Ltd. | Dielectric ceramic composition for high-frequency use and method for producing the same, dielectric ceramic for high-frequency use and method for producing the same, and high-frequency circuit element using the same |
| JP2011162418A (en) * | 2010-02-15 | 2011-08-25 | Ube Industries Ltd | Dielectric ceramic for high frequency, method for producing the same and high frequency circuit element using the same |
| JP6912188B2 (en) * | 2016-11-25 | 2021-08-04 | 京セラ株式会社 | Ceramic porcelain, wiring boards and electronic components |
| CN112979304B (en) * | 2021-04-25 | 2021-08-27 | 北京中科三环高技术股份有限公司 | Microwave dielectric ceramic, preparation method thereof and microwave device |
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