JP3839868B2 - Dielectric ceramic composition and electronic component - Google Patents
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- JP3839868B2 JP3839868B2 JP13518096A JP13518096A JP3839868B2 JP 3839868 B2 JP3839868 B2 JP 3839868B2 JP 13518096 A JP13518096 A JP 13518096A JP 13518096 A JP13518096 A JP 13518096A JP 3839868 B2 JP3839868 B2 JP 3839868B2
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0306—Inorganic insulating substrates, e.g. ceramic, glass
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Description
【０００１】
【発明の属する技術分野】
本発明は、マイクロ波領域で使用され、電子回路基板や電子部品等に適用される誘電体磁器組成物及び、例えば内部および／または表面に導体を有する共振器、コンデンサ、フィルタ等の電子部品に関する。
【０００２】
【従来の技術】
従来より誘電体材料として各種誘電体セラミックスが電子回路基板や電子部品等に広く使用されており、近年、携帯電話に代表される移動体通信等の高周波機器の発展と普及に伴い、高周波領域で使用する電子回路基板や電子部品として誘電体セラミックスが積極的に利用されるようになってきた。
【０００３】
このような誘電体セラミックスからなる電子回路基板等と導体を同時焼成するに際しては、導体が誘電体セラミックスの焼成温度で溶融することがないように、該導体には誘電体セラミックスの焼成温度よりも高い融点を有する、例えば、Ｐｔ、Ｐｄ、Ｗ、Ｍｏ等の金属が用いられていた。
【０００４】
しかしながら、前記金属は導通抵抗が大きいことから、従来の電子回路基板では、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。
【０００５】
そこで係る問題を解消するために導通抵抗の小さいＡｇやＣｕ等の金属を導体として採用し、低温で同時焼成できる誘電体セラミックスが種々提案されている。更に、最近の高周波電子回路基板や電子部品に対する小型化と高性能化の要求に応えるために、特定の周波数領域で比誘電率εｒを高くすることにより共振器の小型化を可能とし、また、誘電体セラミックスのＱ値を高くすることにより、共振器のＱ値も高くすることができて低損失となることから、各種の複合誘電体が提案されている。
【０００６】
従来、例えば、特開平４−２９２４６０号公報に開示された誘電体磁器組成物は、アノーサイト−チタン酸カルシウム系のガラスとＴｉＯ2 からなるもので、低温焼成できるため導体としてＡｇやＣｕ等の金属と同時焼成ができるものであった。
【０００７】
【発明が解決しようとする課題】
しかしながら、前記複合誘電体は、導体として使用するＡｇやＣｕ等の金属と同時焼成できるものの、誘電体セラミックスのＱ値は６ＧＨｚの測定周波数で最大３３０程度（１ＧＨｚ換算では２０００程度）と低く、比誘電率εｒが４〜６ＧＨｚの高周波領域の測定では１６未満と低く、高周波電子回路基板や電子部品の小型化、高性能化には限界があるという課題があった。
【０００８】
本願出願人は、ａＢａＯ・ｂＺｎＯ・ｃＮｂ2 Ｏ5 ・ｄＭｇＯ・ｅＷＯ3 ・ｆＴａ2 Ｏ5 と表わされる誘電体磁器組成物を既に出願しており、この誘電体磁器組成物は、６〜１０ＧＨｚにおいて比誘電率が１９〜３８で、Ｑ値が５００００〜２３００００と高Ｑ値を示すものの、焼成温度が１４００〜１６００℃と高く、一方ガラス等を添加して低温焼成化を図った場合は、Ｑ値等の特性が大きく劣化するという課題があった。
【０００９】
【発明の目的】
本発明は上記課題に鑑みなされたもので、誘電体セラミックスの比誘電率εｒが高く、高Ｑ値を有するとともに、９００〜１０５０℃の比較的低温でＡｇやＣｕ等の導体金属と同時に焼成でき、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誘電体磁器組成物の提供を目的とするものである。
【００１０】
【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、金属元素として少なくともＢａ，Ｚｎ，Ｍｇ，ＷおよびＴａを含有する複合酸化物であって、これらのモル比による組成式をａＢａＯ・ｂＺｎＯ・ｃＮｂ２Ｏ５・ｄＭｇＯ・ｅＷＯ３・ｆＴａ２Ｏ５と表した時、前記ａ、ｂ、ｃ、ｄ、ｅ、ｆが、０．４３≦ａ≦０．６８、０．０１≦ｂ≦０．３０、０≦ｃ≦０．３０、０＜ｄ≦０．３５、０＜ｅ≦０．３５、０＜ｆ≦０．３５、０．５０≦（ｂ＋ｄ）／（ｃ＋ｅ＋ｆ）≦１．６０、ａ＋ｂ＋ｃ＋ｄ＋ｅ＋ｆ＝１を満足する主成分１００重量部に対して、酸化ホウ素を１〜１０重量部、アルカリ金属炭酸塩を１〜１０重量部添加含有してなり、比誘電率が１５以上、Ｑ値が５０００以上の誘電体磁器を得られるものである。
【００１１】
また、本発明の電子部品は、誘電体磁器と、該誘電体磁器の内部および／または表面に形成された導体とを具備する電子部品であって、前記誘電体磁器が、上記した誘電体磁器組成物からなり、かつ、前記導体がＡｇまたはＣｕを主成分とするものである。
【００１２】
【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ＡｇやＣｕ等の導体金属と同時に焼成でき、誘電体セラミックスの比誘電率εｒやＱ値が高く、かつ共振周波数の温度係数τｆを比較的小さくすることができ、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。
【００１３】
そして、本発明においては、硼素含有化合物とアルカリ金属含有化合物を同時に含有するものであるが、これは、上記主成分に対して硼素含有化合物のみを配合した場合には、その配合量が少ないと焼成温度を十分に低下させることができず、ＡｇやＣｕの融点温度以下の温度で焼結させることができない。
【００１４】
また、配合量が多いと焼結温度は低下するが、硼素含有化合物は、焼成時等の高温下で主成分からなる高Ｑ値の結晶相と反応するので、配合量が多すぎた場合は、焼成後において高Ｑ値の結晶相の残存量が少なくなり、高いＱ値を維持することができない。従って、硼素含有化合物のみを添加した場合には、低い焼結温度と高周波領域における誘電特性が共に優れたものを得ることができないからである。
【００１５】
即ち、硼素含有化合物のみを添加した場合は、その添加量がＢ2 Ｏ3 換算で１重量部未満では焼結温度が１０５０℃以下にはならない。また、Ｂ2 Ｏ3 換算で１０重量部よりも多い場合には焼結温度を１０５０℃以下に低下できるが、硼素含有化合物は焼成時等高温下において上述したように高Ｑ値の結晶相と反応するため、Ｑ値が低下してしまうからである。
【００１６】
この組成物の場合、硼素含有化合物の添加による組成物の焼結温度低下効果と焼成後の磁器組成物の誘電特性向上効果とは背反関係にあり、硼素含有化合物のみを添加した組成物では、低い焼結温度と高いＱ値等の優れた誘電特性とを共に備えた組成物を得ることが困難である。
【００１７】
一方、主成分にＬｉ，Ｎａ等のアルカリ金属含有化合物のみを添加した場合には、たとえ添加量を増加させたとしても、組成物の焼結温度を低下させることが殆どできず、１０５０℃以下で焼結できる組成物を得ることができない。
【００１８】
これに対して、硼素含有化合物とアルカリ金属含有化合物とを、各々特定量比で組み合わせ添加配合した本発明の組成物では、硼素含有化合物と高Ｑ値の結晶相との過度の反応が抑制され、かつ、硼素含有化合物のみの添加の場合と比較してさらに焼結温度を低下させることができると同時にＱ値の低下を抑制できるため、ＡｇまたはＣｕを主成分とする金属導体との同時焼成が可能となる。
【００１９】
【発明の実施の形態】
本発明の誘電体磁器組成物は、モル比による組成式をａＢａＯ・ｂＺｎＯ・ｃＮｂ2 Ｏ5 ・ｄＭｇＯ・ｅＷＯ3 ・ｆＴａ2 Ｏ5 と表した時、前記ａ、ｂ、ｃ、ｄ、ｅ、ｆが、０．４３≦ａ≦０．６８、０．０１≦ｂ≦０．３０、０≦ｃ≦０．３０、０＜ｄ≦０．３５、０＜ｅ≦０．３５、０＜ｆ≦０．３５、０．５０≦（ｂ＋ｄ）／（ｃ＋ｅ＋ｆ）≦１．６０、ａ＋ｂ＋ｃ＋ｄ＋ｅ＋ｆ＝１を満足する主成分に、硼素含有化合物とアルカリ金属含有化合物とを各々特定量比で組み合わせ添加配合したものである。
【００２０】
ＢａＯのモル比ａを０．４３≦ａ≦０．６８に設定したのは、０．４３よりも小さい場合、また０．６８よりも大きい場合はＱ値が低下するためである。特に、高Ｑ値とするためには０．５２≦ａ≦０．６２とすることが好ましい。
【００２１】
ＺｎＯのモル比ｂを０．０１≦ｂ≦０．３０に設定したのは、０．０１よりも小さい場合はＱ値が低下し、もしくは焼結性が悪く、また０．３０よりも大きい場合はＱ値が低下するためである。特に高Ｑ値という観点から０．０８≦ｂ≦０．２１とすることが好ましい。
【００２２】
Ｎｂ2 Ｏ5 のモル比ｃを０＜ｃ≦０．３０に設定したのは、０．３０よりも大きい場合はＱ値が低下するためである。特に、高Ｑ値とするためには０．００１≦ｃ≦０．１１とすることが好ましい。
【００２３】
ＭｇＯのモル比ｄを０＜ｄ≦０．３５に設定したのは、０．３５よりも大きい場合はＱ値が低下するためである。特に、高Ｑ値とするためには、０．００１≦ｄ≦０．１５０とすることが好ましい。
【００２４】
ＷＯ3 のモル比ｅを０＜ｅ≦０．３５に設定したのは、０．３５よりも大きい場合はＱ値が低下するためである。特に、高Ｑ値とするためには、０．００１≦ａ≦０．１５とすることが好ましい。
【００２５】
Ｔａ2 Ｏ5 のモル比ｆを０＜ｆ≦０．３５に設定したのは、０．３５よりも大きい場合はＱ値が低下するためである。特に、高Ｑ値とするためには、０．０８≦ｆ≦０．２０が好ましい。
【００２６】
また、０．５０≦（ｂ＋ｄ）／（ｃ＋ｅ＋ｆ）≦１．６０に設定したのは、この範囲外では、Ｑ値が低下するためである。特に０．８〜１．５が望ましい。
【００２７】
そして、本発明の誘電体磁器組成物は、主成分１００重量部に対して、ホウ素含有化合物をＢ2 Ｏ3 換算で１〜１０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重量部添加含有してなるものであるが、このように主成分１００重量部に対して、ホウ素含有化合物をＢ2 Ｏ3 換算で１〜１０重量部添加したのは、ホウ素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、磁器特性が劣化するからである。よって、ホウ素含有化合物の添加量は、主成分１００重量部に対してＢ2 Ｏ3 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３〜８重量部が望ましい。
【００２８】
ホウ素含有化合物としては、Ｂ ２ Ｏ ３ であることが重要である。
【００２９】
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重量部添加含有したのは、アルカリ金属含有化合物の含有量が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、磁器特性が劣化するからである。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で１〜１０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３〜８重量部が望ましい。
【００３０】
アルカリ金属としては、Ｌｉ、Ｋ、Ｎａがあり、アルカリ金属化合物としては、アルカリ金属炭酸塩であることが重要であるが、このうちでも高Ｑ値化および低温焼成化という観点からＬｉが望ましい。
【００３１】
また、本発明においては、誘電体特性に悪影響を及ぼさない範囲でＳｉ、Ｚｎ、Ｍｎ等の酸化物を添加しても良く、この場合、更に低温焼成が可能となる。
【００３２】
本発明の電子部品は、誘電体磁器と、該誘電体磁器の内部および／または表面に形成された導体とを具備する電子部品であって、誘電体磁器が、上述した誘電体磁器組成物からなり、導体が、ＡｇまたはＣｕを主成分とするものである。誘電体磁器と、該誘電体磁器の内部および／または表面に形成された導体とは同時焼成して形成することができる。また、電子部品だけでなく、誘電体磁器と、該誘電体磁器の内部および／または表面に形成された導体とを具備する基板においても、誘電体磁器として上述した誘電体磁器組成物を用いることができる。
【００３３】
本発明の誘電体磁器組成物は、純度９９％以上のＢａＯ，ＺｎＯ，Ｎｂ2 Ｏ5 ，ＭｇＯ、ＷＯ3 及びＴａ2 Ｏ5 の各原料粉末を所定量となるように秤量し、混合粉砕し、これを大気中等の酸化性雰囲気において１０００〜１５００℃の温度で１〜３時間仮焼する。得られた仮焼物に、例えば、Ｂ2 Ｏ3 , Ｌｉ2 ＣＯ3 の各粉末を所定量となるように秤量し、混合粉砕し、プレス成形等により成形した後、大気中または窒素雰囲気中、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。
【００３４】
【実施例】
先ず、純度９９％以上ののＢａＯ，ＺｎＯ，Ｎｂ2 Ｏ5 ，ＭｇＯ、ＷＯ3 及びＴａ2 Ｏ5 の各原料粉末を表１〜表３に示す組成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。
【００３５】
得られた仮焼物にＢ2 Ｏ3 粉末とアルカリ金属化合物を表１〜表３に示す割合となるように秤量し、ＺｒＯ2 ボールを用いたボールミルにて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。
【００３６】
【表１】
【表２】
【表３】
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、引き続いて大気中において表１〜表３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、直径１０ｍｍ、高さ７ｍｍの円柱状の誘電体特性評価用試料を作製した。
【００４０】
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１ＧＨｚにおける１／ｔａｎδ、即ちＱ値（Ｑｆ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４〜６に記載する。
【００４１】
尚、共振周波数の温度係数τｆは、２５℃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、本発明の試料についてはすべて０±３０ｐｐｍ／℃を満足していた。
【００４２】
【表４】
【表５】
【表６】
これらの表４〜表６によれば、本発明の誘電体磁器組成物では、９５０〜１０５０℃の比較的低温で焼成でき、さらに、比誘電率εｒが１５以上、Ｑｆ値が５０００以上の優れた特性を有することが判る。
【００４６】
【発明の効果】
本発明の誘電体磁器組成物は、１０５０℃以下の比較的低温でＡｇやＣｕ等の導体金属と同時に焼成でき、高周波領域において高い比誘電率を有するとともに、Ｑ値も高く、かつ共振周波数の温度特性にも優れ、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が実現できる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a dielectric ceramic composition used in a microwave region and applied to an electronic circuit board, an electronic component, and the like, and an electronic component such as a resonator, a capacitor, and a filter having a conductor inside and / or on the surface. .
[0002]
[Prior art]
Various dielectric ceramics have been widely used as dielectric materials for electronic circuit boards and electronic parts. In recent years, with the development and popularization of high-frequency devices such as mobile communications represented by mobile phones, Dielectric ceramics have been actively used as electronic circuit boards and electronic parts to be used.
[0003]
When simultaneously firing an electronic circuit board or the like made of dielectric ceramics and a conductor, the conductor is not heated at the firing temperature of the dielectric ceramic so that the conductor does not melt at the firing temperature of the dielectric ceramic. For example, metals such as Pt, Pd, W, and Mo having a high melting point have been used.
[0004]
However, since the metal has a large 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.
[0005]
In order to solve the problem, various dielectric ceramics that employ a metal such as Ag or Cu having a low conduction resistance as a conductor and can be fired simultaneously at a low temperature have been proposed. Furthermore, in order to meet the recent demands for miniaturization and high performance of high-frequency electronic circuit boards and electronic components, the resonator can be miniaturized by increasing the relative dielectric constant εr in a specific frequency region, By increasing the Q value of the dielectric ceramic, the Q value of the resonator can also be increased and the loss can be reduced. Therefore, various composite dielectrics have been proposed.
[0006]
Conventionally, for example, a dielectric ceramic composition disclosed in Japanese Patent Laid-Open No. 4-292460 is made of anorthite-calcium titanate glass and TiO 2 , and can be fired at a low temperature. It could be cofired with metal.
[0007]
[Problems to be solved by the invention]
However, although the composite dielectric can be fired simultaneously with a metal such as Ag or Cu used as a conductor, the dielectric ceramic has a low Q value of about 330 at the measurement frequency of 6 GHz (about 2000 in terms of 1 GHz), The measurement in the high frequency region where the dielectric constant εr is 4 to 6 GHz is as low as less than 16, and there is a problem that there is a limit to miniaturization and high performance of high frequency electronic circuit boards and electronic components.
[0008]
Applicant has the dielectric ceramic composition expressed as aBaO · bZnO · cNb 2 O 5 · dMgO · eWO 3 · fTa 2 O 5 have already filed, the dielectric ceramic composition, in 6~10GHz When the relative dielectric constant is 19 to 38 and the Q value is 50000 to 230,000, which is a high Q value, the firing temperature is as high as 1400 to 1600 ° C. There has been a problem that characteristics such as values are greatly deteriorated.
[0009]
OBJECT OF THE INVENTION
The present invention has been made in view of the above problems. The dielectric ceramic has a high dielectric constant εr, a high Q value, and can be fired simultaneously with a conductive metal such as Ag or Cu at a relatively low temperature of 900 to 1050 ° C. An object of the present invention is to provide a dielectric ceramic composition capable of realizing miniaturization and high performance of high-frequency electronic circuit boards and electronic components.
[0010]
[Means for Solving the Problems]
The dielectric ceramic composition of the present invention is a composite oxide containing at least Ba, Zn, Mg, W and Ta as metal elements, and the composition formula based on these molar ratios is expressed as aBaO.bZnO.cNb 2 O 5. When expressed as dMgO · eWO 3 · fTa 2 O 5 , the a, b, c, d, e, and f are 0.43 ≦ a ≦ 0.68, 0.01 ≦ b ≦ 0.30, and 0 ≦. c ≦ 0.30, 0 <d ≦ 0.35, 0 <e ≦ 0.35, 0 <f ≦ 0.35, 0.50 ≦ (b + d) / (c + e + f) ≦ 1.60, a + b + c + d + e + f = 1 1 to 10 parts by weight of boron oxide and 1 to 10 parts by weight of alkali metal carbonate are added to 100 parts by weight of a satisfactory main component, and the dielectric constant is 15 or more and the Q value is 5000 or more. A body porcelain can be obtained.
[0011]
The electronic component of the present invention is an electronic component comprising a dielectric ceramic and a conductor formed inside and / or on the surface of the dielectric ceramic, wherein the dielectric ceramic is the dielectric ceramic described above. It consists of a composition, and the said conductor has Ag or Cu as a main component.
[0012]
[Action]
The dielectric ceramic composition of the present invention can be fired simultaneously with a conductive metal such as Ag or Cu at a relatively low temperature of 900 to 1050 ° C., the dielectric ceramic has a high relative dielectric constant εr and Q value, and a resonance frequency temperature. The coefficient τf can be made relatively small, and the high-frequency electronic circuit board and electronic components can be reduced in size and performance.
[0013]
And, in the present invention, it contains a boron-containing compound and an alkali metal-containing compound at the same time. This is because when only the boron-containing compound is blended with respect to the main component, the blending amount is small. The firing temperature cannot be lowered sufficiently, and sintering cannot be performed at a temperature lower than the melting point temperature of Ag or Cu.
[0014]
In addition, if the amount is too large, the sintering temperature is lowered, but the boron-containing compound reacts with the high-Q crystal phase composed of the main component at a high temperature such as during firing, so if the amount is too large The residual amount of the crystal phase having a high Q value is reduced after firing, and a high Q value cannot be maintained. Therefore, when only a boron-containing compound is added, it is impossible to obtain a material having both a low sintering temperature and excellent dielectric characteristics in a high frequency region.
[0015]
That is, when only a boron-containing compound is added, if the amount added is less than 1 part by weight in terms of B 2 O 3 , the sintering temperature does not become 1050 ° C. or lower. Further, when the amount is more than 10 parts by weight in terms of B 2 O 3 , the sintering temperature can be lowered to 1050 ° C. or lower. However, as described above, the boron-containing compound has a high Q value crystal phase at a high temperature such as firing. This is because the Q value decreases due to the reaction.
[0016]
In the case of this composition, the sintering temperature reduction effect of the composition due to the addition of the boron-containing compound and the dielectric property improvement effect of the ceramic composition after firing are contradictory, and in the composition to which only the boron-containing compound is added, It is difficult to obtain a composition having both a low sintering temperature and excellent dielectric properties such as a high Q value.
[0017]
On the other hand, when only an alkali metal-containing compound such as Li or Na is added to the main component, the sintering temperature of the composition can hardly be lowered even if the addition amount is increased, and it is 1050 ° C. or less. It is not possible to obtain a composition that can be sintered at low temperatures.
[0018]
In contrast, in the composition of the present invention in which a boron-containing compound and an alkali metal-containing compound are added in combination at specific ratios, excessive reaction between the boron-containing compound and the high-Q crystal phase is suppressed. In addition, the sintering temperature can be further reduced as compared with the case of adding only a boron-containing compound, and at the same time, the decrease in the Q value can be suppressed, so that the co-firing with a metal conductor containing Ag or Cu as a main component is possible. Is possible.
[0019]
DETAILED DESCRIPTION OF THE INVENTION
The dielectric ceramic composition of the present invention, when expressed the composition formula by molar ratio aBaO · bZnO · cNb 2 O 5 · dMgO · eWO 3 · fTa 2 O 5, wherein a, b, c, d, e, f is 0.43 ≦ a ≦ 0.68, 0.01 ≦ b ≦ 0.30, 0 ≦ c ≦ 0.30, 0 <d ≦ 0.35, 0 <e ≦ 0.35, 0 <f ≦ 0.35, 0.50 ≦ (b + d) / (c + e + f) ≦ 1.60, a boron-containing compound and an alkali metal-containing compound were added in combination at specific ratios to the main components satisfying a + b + c + d + e + f = 1. Is.
[0020]
The reason why the molar ratio a of BaO is set to 0.43 ≦ a ≦ 0.68 is that the Q value decreases when it is smaller than 0.43 or larger than 0.68. In particular, in order to obtain a high Q value, it is preferable to satisfy 0.52 ≦ a ≦ 0.62.
[0021]
The reason why the molar ratio b of ZnO is set to 0.01 ≦ b ≦ 0.30 is that when it is smaller than 0.01, the Q value is lowered, or the sinterability is poor, and when it is larger than 0.30. Is because the Q value is lowered. In particular, from the viewpoint of a high Q value, 0.08 ≦ b ≦ 0.21 is preferable.
[0022]
The reason why the molar ratio c of Nb 2 O 5 is set to 0 <c ≦ 0.30 is that when it is larger than 0.30, the Q value decreases. In particular, in order to obtain a high Q value, it is preferable to satisfy 0.001 ≦ c ≦ 0.11.
[0023]
The reason why the molar ratio d of MgO is set to 0 <d ≦ 0.35 is that the Q value decreases when it is larger than 0.35. In particular, in order to obtain a high Q value, it is preferable to satisfy 0.001 ≦ d ≦ 0.150.
[0024]
The reason why the molar ratio e of WO 3 is set to 0 <e ≦ 0.35 is that when it is larger than 0.35, the Q value decreases. In particular, in order to obtain a high Q value, it is preferable to satisfy 0.001 ≦ a ≦ 0.15.
[0025]
The reason why the molar ratio f of Ta 2 O 5 is set to 0 <f ≦ 0.35 is that when it is larger than 0.35, the Q value decreases. In particular, in order to obtain a high Q value, 0.08 ≦ f ≦ 0.20 is preferable.
[0026]
The reason why 0.50 ≦ (b + d) / (c + e + f) ≦ 1.60 is set is that the Q value decreases outside this range. 0.8 to 1.5 is particularly desirable.
[0027]
The dielectric ceramic composition of the present invention is 1 to 10 parts by weight of the boron-containing compound in terms of B 2 O 3 and 1 to 10 parts of the alkali metal-containing compound in terms of alkali metal carbonate with respect to 100 parts by weight of the main component. Although 10 parts by weight is added and contained, 1 to 10 parts by weight of the boron-containing compound in terms of B 2 O 3 is added to 100 parts by weight of the main component as described above. When the amount is less than 1 part by weight, sintering does not occur even at 1100 ° C., and co-firing with Ag or Cu cannot be performed. Conversely, when the amount exceeds 10 parts by weight, the crystal phase changes and the ceramic characteristics deteriorate. Because. Therefore, the addition amount of the boron-containing compound is specified as 1 to 10 parts by weight in terms of B 2 O 3 with respect to 100 parts by weight of the main component, and particularly 3 to 8 parts by weight from the viewpoint of the Q value of the dielectric ceramic. Is desirable.
[0028]
It is important that the boron-containing compound is B 2 O 3 .
[0029]
In addition, the addition of 1 to 10 parts by weight of the alkali metal-containing compound in terms of alkali metal carbonate does not sinter even at 1100 ° C. when the content of the alkali metal-containing compound is less than 1 part by weight. This is because simultaneous firing with Cu is not possible, and conversely, when the amount exceeds 10 parts by weight, the crystal phase changes and the ceramic characteristics deteriorate. Therefore, the addition amount of the alkali metal-containing compound is specified as 1 to 10 parts by weight in terms of alkali metal carbonate with respect to 100 parts by weight of the main component, and particularly 3 to 8 parts by weight from the viewpoint of the Q value of the dielectric ceramic. Is desirable.
[0030]
Examples of the alkali metal include Li, K, and Na. As the alkali metal compound, it is important that the alkali metal compound is an alkali metal carbonate , and among these, Li is desirable from the viewpoint of high Q value and low temperature firing.
[0031]
In the present invention, oxides such as Si, Zn and Mn may be added as long as the dielectric properties are not adversely affected. In this case, further low-temperature firing is possible.
[0032]
The electronic component of the present invention is an electronic component comprising a dielectric ceramic and a conductor formed in and / or on the surface of the dielectric ceramic, wherein the dielectric ceramic is from the above-described dielectric ceramic composition. Thus, the conductor is mainly composed of Ag or Cu. The dielectric ceramic and the conductor formed inside and / or on the surface of the dielectric ceramic can be formed by simultaneous firing. In addition to electronic components, the dielectric ceramic composition described above is used as a dielectric ceramic in a substrate including a dielectric ceramic and a conductor formed in and / or on the surface of the dielectric ceramic. Can do.
[0033]
The dielectric ceramic composition of the present invention weighs each raw material powder of BaO, ZnO, Nb 2 O 5 , MgO, WO 3 and Ta 2 O 5 having a purity of 99% or more to a predetermined amount, and mixes and grinds them. This is calcined at a temperature of 1000 to 1500 ° C. for 1 to 3 hours in an oxidizing atmosphere such as air. In the obtained calcined product, for example, each powder of B 2 O 3 , Li 2 CO 3 is weighed so as to be a predetermined amount, mixed and pulverized, molded by press molding or the like, and then in the atmosphere or nitrogen atmosphere, It is obtained by baking at 900 to 1050 ° C. for 0.5 to 2.0 hours.
[0034]
【Example】
First, each raw material powder of BaO, ZnO, Nb 2 O 5 , MgO, WO 3 and Ta 2 O 5 with a purity of 99% or more is weighed to have the composition shown in Tables 1 to 3, After adding pure water as a medium and mixing with a ball mill using ZrO 2 balls for 24 hours, the mixture was dried, and then the dried product was calcined in the atmosphere at a temperature of 1200 ° C. for 1 hour.
[0035]
The resulting calcined product into B 2 O 3 powder and an alkali metal compound were weighed so that the ratio shown in Table 1 to Table 3 for 24 hours in a ball mill using ZrO 2 balls, after mixing, polyvinyl as a binder After adding 1% by weight of alcohol, the mixture was granulated, and the granulated product was press-molded with an applied pressure of about 1 t / cm 2 to form a cylindrical molded body having a diameter of about 12 mm and a height of 10 mm.
[0036]
[Table 1]
[Table 2]
[Table 3]
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 to 3 for 60 minutes. Both end surfaces of the cylindrical body thus obtained were polished to prepare a cylindrical dielectric characteristic evaluation sample having a diameter of 10 mm and a height of 7 mm.
[0040]
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 the relative permittivity εr of each sample and 1 / tan δ at 1 GHz, that is, the Q value ( Qf value) and the temperature coefficient τf of the resonance frequency in the temperature range of −40 to + 85 ° C. were measured. These results are listed in Tables 4-6.
[0041]
The temperature coefficient τf of the resonance frequency was calculated as 0-40 ppm / ° C for all the samples of the present invention as a result of calculating the temperature coefficient τf of the resonance frequency at -40 ° C and + 85 ° C with reference to the resonance frequency of 25 ° C. I was satisfied.
[0042]
[Table 4]
[Table 5]
[Table 6]
According to Tables 4 to 6, the dielectric ceramic composition of the present invention can be fired at a relatively low temperature of 950 to 1050 ° C., and further has an excellent relative dielectric constant εr of 15 or more and Qf value of 5000 or more. It can be seen that it has the characteristics.
[0046]
【The invention's effect】
The dielectric ceramic composition of the present invention can be fired simultaneously with a conductor metal such as Ag or Cu at a relatively low temperature of 1050 ° C. or less, has a high relative dielectric constant in a high frequency region, has a high Q value, and has a resonance frequency. It also has excellent temperature characteristics and can achieve further miniaturization and higher performance of high-frequency electronic circuit boards and electronic components.
Claims (3)
ａＢａＯ・ｂＺｎＯ・ｃＮｂ２Ｏ５・ｄＭｇＯ・ｅＷＯ３・ｆＴａ２Ｏ５
と表した時、前記ａ、ｂ、ｃ、ｄ、ｅ、ｆが
０．４３≦ａ≦０．６８
０．０１≦ｂ≦０．３０
０≦ｃ≦０．３０
０＜ｄ≦０．３５
０＜ｅ≦０．３５
０＜ｆ≦０．３５
０．５０≦（ｂ＋ｄ）／（ｃ＋ｅ＋ｆ）≦１．６０
ａ＋ｂ＋ｃ＋ｄ＋ｅ＋ｆ＝１
を満足する主成分１００重量部に対して、酸化ホウ素を１〜１０重量部、アルカリ金属炭酸塩を１〜１０重量部添加含有してなり、比誘電率が１５以上、Ｑ値が５０００以上の誘電体磁器を得られることを特徴とする誘電体磁器組成物。A composite oxide containing at least Ba, Zn, Mg, W, and Ta as a metal element, and a composition formula based on a molar ratio thereof is aBaO · bZnO · cNb 2 O 5 · dMgO · eWO 3 · fTa 2 O 5
Where a, b, c, d, e, f are 0.43 ≦ a ≦ 0.68.
0.01 ≦ b ≦ 0.30
0 ≦ c ≦ 0.30
0 <d ≦ 0.35
0 <e ≦ 0.35
0 <f ≦ 0.35
0.50 ≦ (b + d) / (c + e + f) ≦ 1.60
a + b + c + d + e + f = 1
1 to 10 parts by weight of boron oxide and 1 to 10 parts by weight of alkali metal carbonate are added to 100 parts by weight of the main component satisfying the above, and the relative dielectric constant is 15 or more and the Q value is 5000 or more. A dielectric ceramic composition characterized in that a dielectric ceramic is obtained.
ａＢａＯ・ｂＺｎＯ・ｃＮｂ２Ｏ５・ｄＭｇＯ・ｅＷＯ３・ｆＴａ２Ｏ５
と表した時、前記ａ、ｂ、ｃ、ｄ、ｅ、ｆが
０．４３≦ａ≦０．６８
０．０１≦ｂ≦０．３０
０≦ｃ≦０．３０
０＜ｄ≦０．３５
０＜ｅ≦０．３５
０＜ｆ≦０．３５
０．５０≦（ｂ＋ｄ）／（ｃ＋ｅ＋ｆ）≦１．６０
ａ＋ｂ＋ｃ＋ｄ＋ｅ＋ｆ＝１
を満足する主成分１００重量部に対して、ホウ素をＢ２Ｏ３換算で１〜１０重量部、アルカリ金属をアルカリ金属炭酸塩換算で１〜１０重量部添加含有してなり、比誘電率が１５以上、Ｑ値が５０００以上、かつ、前記導体がＡｇまたはＣｕを主成分とすることを特徴とする電子部品。An electronic component comprising a dielectric ceramic and a conductor formed in and / or on the surface of the dielectric ceramic, wherein the dielectric ceramic contains at least Ba, Zn, Mg, W and Ta as metal elements. a composite oxide containing, 2 aBaO · bZnO · cNb the formula by these molar ratio O 5 · dMgO · eWO 3 · fTa 2 O 5
Where a, b, c, d, e, f are 0.43 ≦ a ≦ 0.68.
0.01 ≦ b ≦ 0.30
0 ≦ c ≦ 0.30
0 <d ≦ 0.35
0 <e ≦ 0.35
0 <f ≦ 0.35
0.50 ≦ (b + d) / (c + e + f) ≦ 1.60
a + b + c + d + e + f = 1
Relative to 100 parts by weight of the main component which satisfies, 1-10 parts by weight of boron in terms of B 2 O 3, becomes the alkali metals contained added to 10 parts by weight of an alkali metal carbonate terms, dielectric An electronic component having a rate of 15 or more, a Q value of 5000 or more, and the conductor containing Ag or Cu as a main component.
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| JP13518096A JP3839868B2 (en) | 1996-05-29 | 1996-05-29 | Dielectric ceramic composition and electronic component |
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