JP3597244B2 - Dielectric porcelain composition - Google Patents
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Description
【０００１】
【産業上の利用分野】
本発明は高周波領域で使用される各種フィルタや共振器等に使用される誘電体磁器組成物に関するものである。
【０００２】
【従来の技術】
近年、自動車電話や携帯電話、または衛星放送など、マイクロ波領域の電磁波を利用する通信の進展にともない、端末機器の小型化への要求がますます強くなっている。端末機器を小型化するためには、機器を構成する個々の部品を小型化する必要がある。誘電体磁器はこれらの機器において、各種フィルタや共振器として組み込まれている。これらの共振デバイスの大きさは同じ共振モードを利用する場合、使用する誘電体材料の持つ比誘電率（εr）の平方根に逆比例するため、小型の共振デバイスを作製するには、高い比誘電率を有する材料が必要である。また、誘電体磁器用の誘電体材料に求められる他の特性は、マイクロ波領域で低損失であること、すなわちＱ値が高いこと、さらに共振周波数の温度係数（τf）が小さいことである。ここでＱ値とは、誘電損失ｔａｎδの逆数をいう。
【０００３】
比誘電率の大きい材料として、（Ｐｂ，Ｃａ）ＺｒＯ3系が特開平４−６５０２１号公報に提案されている。この系は１００を越える高い比誘電率と、２〜４ＧＨｚで８００程度の高いＱ値、および小さい共振周波数の温度係数を有している。
【０００４】
一方、導体と誘電体磁器を積層構造にし、共振デバイスを小型、高機能化しようとする試みが行なわれている。導体は、マイクロ波のような高周波領域で使用する場合、導電率が高い必要があるため、Ｃｕ、Ａｕ、Ａｇ、またはそれらの合金を使用する必要がある。また、誘電体磁器は積層構造にする場合、導体の金属と同時に焼成する必要があるため、導体金属が溶解せず、かつ酸化しない焼成条件で緻密に焼結しなければならない。すなわち、用いる導体金属の融点（Ｃｕの場合１０８３℃、Ａｕの場合１０６３℃、Ａｇの場合９６１℃）以下の低温で、かつＣｕを電極に用いる場合は低い酸素分圧での焼成が必要となる。低温で焼結できるマイクロ波誘電体磁器として、Ｂｉ2Ｏ3−ＣａＯ−Ｎｂ2Ｏ5系が米国特許第５，２７３，９４４号明細書に提案されている。
【０００５】
【発明が解決しようとする課題】
しかし、前記従来のＢｉ2Ｏ3−ＣａＯ−Ｎｂ2Ｏ5系の磁器は、１０００℃程度の低温で焼結できるが、主成分のＢｉ2Ｏ3が焼成時に蒸発するため、焼成温度に対して誘電特性が不安定であるという問題があった。
【０００６】
本発明は、前記従来の問題を解決するため、第１成分にＢｉ2Ｏ3を含まず、低温で焼結し、比誘電率が高く、高いＱ値と小さい共振周波数の温度係数を有する誘電体磁器組成物を提供することを目的としている。
【０００７】
【課題を解決するための手段】
前記目的を達成するため、本発明の第１番目の誘電体磁器組成物は、一般式Ｃａ｛（Ｍｇ1/3Ｎｂ2/3）1-xＴｉx｝Ｏ3（ただし、０≦ｘ≦０．５０）で表される第１成分と、少なくともＳｉＯ2 とＢ2Ｏ3とＡｌ 2 Ｏ 3 とを含む第２成分からなる誘電体磁器組成物であって、
前記第１成分の誘電体磁器組成物全体に占める割合が４０重量％以上９８重量％以下、
かつ前記第２成分の誘電体磁器組成物全体に占める割合が２重量％以上６０重量％以下の範囲であり、第２成分全体に占める第２成分の各組成の割合が、３０〜６５重量％の範囲のＳｉＯ2、１０〜３５重量％の範囲のＢ2Ｏ3、５〜３０重量％の範囲のＡｌ2Ｏ3、０〜８重量％の範囲のＺｒＯ2、及び０〜１３重量％の範囲のＭＯ（Ｍは、Ｃａ、Ｓｒ、Ｂａから選ばれる少なくとも一種の元素）であることを特徴とする。
【０００８】
本発明の第２番目の誘電体磁器組成物は、一般式Ｃａ｛（Ｍｇ1/3Ｎｂ2/3）1-xＴｉx｝Ｏ3（ただし、０≦ｘ≦０．５０）で表される組成物とＡｌ 2 Ｏ 3 とからなる第１成分と、少なくともＳｉＯ2 とＢ2Ｏ3 とＡｌ 2 Ｏ 3 とを含む第２成分とを混合して焼成した誘電体磁器組成物であって、
前記第１成分の誘電体磁器組成物全体に占める割合が３０重量％以上９８重量％以下の範囲であり、第１成分全体に占めるＡｌ 2 Ｏ 3 の割合が０重量％を超え８０重量％以下であり、
かつ第２成分の誘電体磁器組成物全体に占める割合が２重量％以上７０重量％以下の範囲であり、第２成分全体に占める第２成分の各組成の割合が、３０〜６５重量％の範囲のＳｉＯ2、１０〜３５重量％の範囲のＢ2Ｏ3、５〜３０重量％の範囲のＡｌ2Ｏ3、０〜８重量％の範囲のＺｒＯ2、及び０〜１３重量％の範囲のＭＯ（Ｍは、Ｃａ、Ｓｒ、Ｂａから選ばれる少なくとも一種の元素）であることを特徴とする。
【０００９】
【作用】
本発明の第１番目の誘電体磁器組成物によれば、第１成分として比誘電率が高く、優れたマイクロ波誘電特性を持つＣａ｛（Ｍｇ1/3Ｎｂ2/3）1-XＴｉX｝Ｏ3（ただし、０≦ｘ≦０．５０）を用い、第２成分に焼結を促進するガラス成分を含有しているため、１０００℃程度で焼結し、比誘電率が高く、高いＱ値と小さい共振周波数の温度係数を有する誘電体磁器を実現できる。また、第１成分にＢｉ2Ｏ3を含まないため、焼成温度に対する誘電特性の安定性も優れている。
【００１０】
本発明の第２番目の誘電体磁器組成物によれば、第１成分としてＣａ｛（Ｍｇ1/3Ｎｂ2/3）1-XＴｉX｝Ｏ3（ただし、０≦ｘ≦０．５０）に加え、比誘電率の低い酸化アルミニウムを含ませることにより、焼結温度、Ｑ値、および温度係数を悪化させることなく比誘電率を調節することが可能である。また、第２成分に融点を下げたガラス質成分を添加するため、１０００℃程度で焼結し、比誘電率が高く、高いＱ値と小さい共振周波数の温度係数を有する誘電体磁器を実現できる。
【００１１】
さらに、前記本発明の第１〜２番目の誘電体磁器組成物によれば、第２成分が３０〜６５重量％の範囲のＳｉＯ2、１０〜３５重量％の範囲のＢ2Ｏ3、５〜３０重量％の範囲のＡｌ2Ｏ3、０〜８重量％の範囲のＺｒＯ2、及び０〜１３重量％の範囲のＭＯ（Ｍは、Ｃａ、Ｓｒ、Ｂａから選ばれる少なくとも一種の元素）からなるので、さらに低温焼結が可能で、高い比誘電率、高いＱｆ積、小さい共振周波数の温度係数と優れたマイクロ波誘電特性をもつ誘電体磁器組成物を実現できる。
【００１２】
また前記において、誘電体磁器組成物の比誘電率（εr）が１４〜４０、Ｑｆ積が１０００〜３００００ＧＨｚ、共振周波数の温度係数（τf）が−５０〜＋５０ppm/℃の範囲、または誘電体磁器組成物の比誘電率（εr）が９〜２４、Ｑｆ積が１０００〜３００００ＧＨｚ、共振周波数の温度係数（τf）が−５０〜＋５０ppm/℃の範囲であるという好ましい例によれば、積層型マイクロ波共振デバイスが実現でき、フィルタや共用器などの高周波デバイスの小型化と高性能化が可能となる。
【００１３】
また本発明の誘電体組成物を用いると、Ａｕ，Ａｇ，Ｃｕ等を内部導体に用いた積層型マイクロ波共振デバイスが実現でき、フィルタや共用器などの高周波デバイスの小型化と高性能化が可能となる。
【００１４】
【実施例】
以下、実施例を用いて本発明をさらに具体的に説明する。
【００１５】
（実施例１）
実施例１は本発明の第１発明の一実施例に対応するものである。
まず、第１成分として用いる粉末の合成について述べる。出発原料には化学的に高純度（９９重量％以上）であるＣａＣＯ3、ＭｇＯ、Ｎｂ2Ｏ5、およびＴｉＯ2を用いた。原料の純度補正を行なった後、組成をＣａ｛（Ｍｇ1/3Ｎｂ2/3）1-XＴｉX｝Ｏ3と表したときのｘが所定の値になるように秤量した。これらの粉体を、ジルコニアの玉石および純水とともにボールミルで１７時間混合した。混合後、スラリーを乾燥し、アルミナ製の坩堝にいれ、温度１０００〜１３００℃で２時間仮焼した。仮焼体を、解砕した後、前述したボールミルで１７時間粉砕し、乾燥させ、第１成分の粉末とした。
【００１６】
次に、第２成分として用いる粉末の合成について述べる。出発原料には化学的に高純度（９９重量％以上）であるＳｉＯ2、Ｂ2Ｏ3、Ａｌ2Ｏ3、ＺｒＯ2、ＢａＣＯ3、ＳｒＣＯ3、ＣａＣＯ3、Ｌｉ2Ｏ、ＺｎＯ、およびＰｂＯを用いた。原料の純度補正を行なったのち、表１に示した種々の組成となるように秤量した。これらの粉体を、エタノールを溶媒に用いてボールミル混合を行い、乾燥させた。混合粉体を坩堝にいれ、温度１０００〜１２００℃で溶融させ、急冷した。解砕した後、混合と同様の方法にて粉砕し、乾燥させ、第２成分の粉末とした。合成した第２成分の組成を表１に示す。
【００１７】
【表１】
第１成分と第２成分の粉末は、ボールミルにて湿式混合し、乾燥させた。得られた粉体にバインダとしてポリビニルアルコールの５重量％水溶液を６重量％加えて混合後、３２メッシュのふるいを通して造粒し、１００ＭＰａで直径１３ｍｍ、厚み約５ｍｍの円柱状にプレス成形した。成形体を温度６００℃で３時間加熱してバインダを焼却後、マグネシア製の磁器容器に入れ、蓋をし、温度８００〜１４００℃の種々の温度で２時間保持して焼成した。密度が最高となる温度で焼成した焼結体についてマイクロ波での誘電特性を測定した。共振周波数とＱ値は、誘電体共振器法により求めた。焼結体の寸法と共振周波数より比誘電率（εr）を算出した。共振周波数は４から８ＧＨｚであった。また、−２５℃、２０℃及び８５℃における共振周波数を測定し、最小二乗法により、その温度係数（τf）を算出した。結果を表２に示す。ここで表２におけるＱｆ積とは、Ｑ値とこれを測定した時の周波数ｆの積をいう。ここで、周波数ｆは４〜８ＧＨｚの間で、資料の大きさや形状などにより変化する。そこで、Ｑｆ積とすることにより、資料の大きさや形状などに影響されない値として算出した。この方法は当業者にとって一般的に行われている方法である。
【００１９】
【表２】
表２より、本実施例の組成の磁器は、８５０〜１１５０℃の範囲の温度で焼結し、１４〜４０の範囲の比誘電率（εr）、１２００〜１８０００ＧＨｚの範囲のＱｆ積、−４１から＋４８ppm/℃の共振周波数の温度係数（τf）と優れたマイクロ波誘電特性をもつことが確認できた。第２成分の組成は、試料番号１０から１３の例に示したように、様々な組成でも優れた誘電特性を実現させることができることから、少なくともＳｉＯ2、Ｂ2Ｏ3のうちの一種以上を含んでいれば良いことが確認できた。
【００２１】
試料番号４の例に示したように第１成分のＣａ｛（Ｍｇ1/3Ｎｂ2/3）1-XＴｉX｝Ｏ3におけるｘが０．５を越えると、共振周波数の温度係数が＋５０ppm/℃を越える大きい値となり実用上好ましくない。試料番号５の例のように第２成分の量が２重量％未満であると、焼成温度が１４００℃と高く、本発明の目的にそぐわない。また、試料番号９の例のように、第２成分の量が６０重量％を越えると、Ｑｆ積が１０００ＧＨｚ以下の小さい値となるので望ましくない。
【００２２】
（実施例２）
実施例２は本発明の第１発明の別の実施例に対応するものである。
試料の合成、特性の評価については実施例１と同様の方法により行った。ただし、第２成分の組成については表３に示したものを用いた。結果を表４に示す。
【００２３】
【表３】
【表４】
表４より、クレーム２の範囲内の誘電体磁器は、８７５〜９５０℃の範囲の温度で焼結し、１９〜３３の範囲の比誘電率（εr）、２８００〜５１００ＧＨｚの範囲のＱｆ積、−１０から＋４１ppm/℃の範囲の共振周波数の温度係数（τf）と優れたマイクロ波誘電特性をもつことが確認できた。
【００２６】
ＳｉＯ2が３０重量％未満の第２成分Ｉを用いた試料番号２０の例、Ｂ2Ｏ3が３５重量％より多い第２成分Ｌを用いた試料番号２３の例、およびＡｌ2Ｏ3が５重量％より少ない第２成分Ｍを用いた試料番号２４の例では、Ｑf積が１０００ＧＨｚより小さくなるので好ましくない。また、ＳｉＯ2が６５重量％より多い第２成分Ｊを用いた試料番号２１の例、Ｂ2Ｏ3が１０重量％より少ない第２成分Ｋを用いた試料番号２２の例、Ａｌ2Ｏ3が３０重量％より多い第２成分Ｎを用いた試料番号２５の例、ＺｒＯ2が８重量％より多い第２成分Ｏを用いた試料番号２６の例、およびＭＯ（Ｍは、Ｃａ、Ｓｒ、Ｂａのうちより選ばれる一種以上）が１３重量％より多い第２成分Ｐを用いた試料番号２７の例では、焼成温度が１１００℃以上と高かったので、好ましくなかった。
【００２７】
（実施例３）
実施例３は本発明の第２番目の発明の一実施例に対応するものである。
試料の合成、特性の評価については実施例１と同様の方法により行った。第１成分が、Ｃａ｛（Ｍｇ1/3Ｎｂ2/3）1-XＴｉX｝Ｏ3に加え、Ａｌ2Ｏ3を含む。ただし、第２成分の組成については表１に示したものを用いた。結果を表５に示す。
【００２８】
【表５】
表５より本実施例の誘電体磁器は、８５０〜１１５０℃の範囲の温度で焼結し、９〜２４の範囲の比誘電率（εr）、１４００〜１２０００ＧＨｚの範囲のＱｆ積、−２２から＋４６ppm/℃の範囲の共振周波数の温度係数（τf）と優れたマイクロ波誘電特性をもつことが確認できた。比誘電率は第１成分中のＡｌ2Ｏ3の量Ｗを増やすと低下させることができた。
【００３０】
試料番号３３の例に示したように、第２成分の量が２重量％より少ないと１４００℃以下の温度では焼結しないので好ましくない。試料番号３８の例に示したように、第２成分の量が７０重量％より多いとＱｆ積が１０００ＧＨｚより小さくなり好ましくない。試料番号４０の例に示したように、第１成分がすべてＡｌ2Ｏ3の場合共振周波数の温度係数が−５０ppm/℃より負に大きい値となり好ましくない。また、試料番号４２の例に示したように第１成分のＣａ｛（Ｍｇ1/3Ｎｂ2/3）1-XＴｉX｝Ｏ3におけるｘが０．５を越えると、共振周波数の温度係数が＋５０ppm/℃を越える正の大きい値となり実用上好ましくない。
【００３１】
（実施例４）
実施例４は本発明の第２番目の発明の別の実施例に対応するものである。試料の合成、特性の評価については実施例１と同様の方法により行った。ただし、第２成分の組成については表３に示したものを用いた。結果を表６に示す。
【００３２】
【表６】
表６より、本実施例の誘電体磁器は、８７５〜９７５℃の範囲の温度で焼結し、１１〜２４の範囲の比誘電率（εr）、３２００〜５３００ＧＨｚの範囲のＱｆ積、−１６から＋３７ppm/℃の範囲の共振周波数の温度係数（τf）と優れたマイクロ波誘電特性をもつことが確認できた。
【００３４】
ＳｉＯ2が３０重量％より少ない第２成分Ｉを用いた試料番号５１の例、Ｂ2Ｏ3が３５重量％より多い第２成分Ｌを用いた試料番号５４の例、およびＡｌ2Ｏ3が５重量％より少ない第２成分Ｍを用いた試料番号５５の例では、Ｑf積が１０００ＧＨｚより小さくなるので好ましくない。また、ＳｉＯ2が６５重量％より多い第２成分Ｊを用いた試料番号５２の例、Ｂ2Ｏ3が１０重量％より少ない第２成分Ｋを用いた試料番号５３の例、Ａｌ2Ｏ3が３０重量％より多い第２成分Ｎを用いた試料番号５６の例、ＺｒＯ2が８重量％より多い第２成分Ｏを用いた試料番号５７の例、およびＭＯ（Ｍは、Ｃａ、Ｓｒ、Ｂａのうちより選ばれる一種以上）が１３重量％より多い第２成分Ｐを用いた試料番号５８の例では、焼成温度が１１００℃を越えるので好ましくない。
なお、前記実施例以外の元素の含有も、本発明の範囲であれば誘電特性に悪い影響を与えない限り使用することができる。
【００３５】
（参考例１）
以下図面を用いて本発明の誘電体磁器を用いた積層型の共振デバイスの一例を説明する。図１は本発明の一実施例の誘電体組成物１を用い、Ａｕ、Ａｇ、Ｃｕ等からなる内部導体を設け、かつ外部導体５、６、７を設けた積層型マイクロ波共振デバイスの斜視図である。図１に示す積層型マイクロ波共振デバイスの一例のディメンジョンは、縦８ｍｍ、横５ｍｍ、高さ２．５ｍｍである。図２は図１のＩ−Ｉ線断面図、図３は図１のII−II線断面図、図４（ａ）は図２のIII−III線断面図、図４（ｂ）は図２のIV−IV線断面図、図４（ｃ）は図２のV−V線断面図であり、誘電体組成物１の内部に、Ａｕ、Ａｇ、Ｃｕ等の内部導体２、３、４と外部導体５の配置を示している。内部導体３は、幅１ｍｍ、長さ７ｍｍ、厚さ０．０３ｍｍ（３０μｍ）とした。内部導体２と３はスクリーンプリント法によって形成した。内部導体２と３の間はコンデンサー（capacitor）として機能する。このコンデンサー（capacitor）を介して、マイクロ波が共振デバイスへ導 入され、特定の周波数を持つマイクロ波のみが共振し、共振器として機能する。
【００３６】
【発明の効果】
以上説明した通り、本発明の第１番目の誘電体磁器組成物によれば、第１成分として比誘電率が高く、優れたマイクロ波誘電特性を持つＣａ｛（Ｍｇ1/3Ｎｂ2/3）1-XＴｉX｝Ｏ3（ただし、０≦ｘ≦０．５０）を用い、第２成分に焼結を促進するガラス成分を含有しているため、１０００℃程度で焼結し、比誘電率が高く、高いＱ値と小さい共振周波数の温度係数を有する誘電体磁器を実現できる。また、第１成分にＢｉ2Ｏ3を含まないため、焼成温度に対する誘電特性の安定性も優れている。
【００３７】
また本発明の第２番目の誘電体磁器組成物によれば、第１成分としてＣａ｛（Ｍｇ1/3Ｎｂ2/3）1-XＴｉX｝Ｏ3（ただし、０≦ｘ≦０．５０）に加え、比誘電率の低い酸化アルミニウムを含ませることにより、焼結温度、Ｑ値、および温度係数を悪化させることなく比誘電率を調節することが可能である。また、第２成分に融点を下げたガラス質成分を添加するため、１０００℃程度で焼結し、比誘電率が高く、高いＱ値と小さい共振周波数の温度係数を有する誘電体磁器を実現できる。
【００３８】
また、本発明の第１〜２番目の誘電体磁器組成物によると、１０００℃前後の低温で焼結でき、比誘電率が１５前後または２５前後と高いときに、高いＱ値と小さいτfを実現できるため、Ｃｕ、Ａｕ、あるいはＡｇなどを内部導体に用いた積層型の共振デバイスを実現できる。これにより、フィルタや共用器などの高周波デバイスの小型化と高機能化が可能となる。また、本発明の誘電体磁器は、共振デバイスのみならず、マイクロ波用の回路基板、磁器積層コンデンサなどにも利用でき、工業的価値が大きいものである。
【図面の簡単な説明】
【図１】本発明の一実施例の誘電体組成物を用いた積層型マイクロ波共振デバイスの斜視図である。
【図２】図１のＩ−Ｉ線断面図である。
【図３】図１のII−II線断面図である。
【図４】図４（ａ）は図２のIII−III線断面図、図４（ｂ）は図２のIV−IV線断面図、図４（ｃ）は図２のV−V線断面図である。
【符号の説明】
１ 誘電体組成物
２，３，４ 内部導体
５，６，７ 外部導体[0001]
[Industrial applications]
The present invention relates to a dielectric ceramic composition used for various filters and resonators used in a high frequency range.
[0002]
[Prior art]
In recent years, with the development of communication using electromagnetic waves in the microwave region, such as automobile telephones, mobile telephones, and satellite broadcasting, there is an increasing demand for miniaturization of terminal devices. In order to reduce the size of a terminal device, it is necessary to reduce the size of individual components constituting the device. In these devices, dielectric porcelain is incorporated as various filters and resonators. When using the same resonance mode, the size of these resonance devices is inversely proportional to the square root of the relative permittivity (ε r ) of the dielectric material to be used. A material having a dielectric constant is required. Further, other characteristics required for the dielectric material for dielectric porcelain are low loss in a microwave region, that is, a high Q value and a small temperature coefficient (τ f ) of the resonance frequency. . Here, the Q value refers to the reciprocal of the dielectric loss tan δ.
[0003]
As a material having a large relative dielectric constant, a (Pb, Ca) ZrO 3 system has been proposed in Japanese Patent Application Laid-Open No. 4-65021. This system has a high relative dielectric constant of over 100, a high Q value of about 800 at 2 to 4 GHz, and a low resonance frequency temperature coefficient.
[0004]
On the other hand, attempts have been made to make the resonance device compact and highly functional by forming the conductor and the dielectric porcelain in a laminated structure. When the conductor is used in a high-frequency region such as microwaves, it is necessary to use Cu, Au, Ag, or an alloy thereof because the conductivity needs to be high. Further, when the dielectric porcelain has a laminated structure, it must be fired at the same time as the metal of the conductor, and therefore must be densely sintered under firing conditions in which the conductor metal does not melt and is not oxidized. That is, firing at a low temperature of not more than the melting point of the conductive metal used (1083 ° C. for Cu, 1063 ° C. for Au, 961 ° C. for Ag) and a low oxygen partial pressure when Cu is used for the electrodes are required. . As a microwave dielectric ceramic that can be sintered at a low temperature, Bi 2 O 3 -CaO-Nb 2
[0005]
[Problems to be solved by the invention]
However, the above-mentioned conventional Bi 2 O 3 —CaO—Nb 2 O 5 porcelain can be sintered at a low temperature of about 1000 ° C., but the main component Bi 2 O 3 evaporates at the time of firing. Therefore, there is a problem that the dielectric characteristics are unstable.
[0006]
In order to solve the above-mentioned conventional problems, the present invention does not include Bi 2 O 3 as a first component, sinters at a low temperature, has a high relative dielectric constant, has a high Q value, and has a temperature coefficient of a small resonance frequency. It is intended to provide a body porcelain composition.
[0007]
[Means for Solving the Problems]
In order to achieve the above object, the first dielectric ceramic composition of the present invention has a general formula of Ca ｛(Mg 1/3 Nb 2/3 ) 1-x Ti x ｝ O 3 (where 0 ≦ x ≦ a first component represented by 0.50), a dielectric ceramic composition comprising a second component comprising at least SiO 2, B 2 O 3 and Al 2 O 3,
The proportion of the first component in the whole dielectric ceramic composition is 40% by weight or more and 98% by weight or less;
The proportion of the second component in the whole dielectric ceramic composition is in the range of 2% to 60% by weight, and the proportion of each composition of the second component in the whole second component is 30 to 65% by weight. SiO 2 range of 10 to 35 wt% of the B 2 O 3, of from 5 to 30 wt% Al 2 O 3, ZrO 2 in the range of 0-8 wt%, and 0-13 wt% MO (M is at least one element selected from Ca, Sr, and Ba) in the range.
[0008]
The second dielectric ceramic composition of the present invention have the general formula Ca {(Mg 1/3 Nb 2/3) 1-x Ti x} O 3 ( however, 0 ≦ x ≦ 0.50) is expressed in a first component comprising the composition and Al 2 O 3 Prefecture that, and at least SiO 2, B 2 O 3 and Al 2 O 3 and the dielectric ceramic composition obtained by firing a mixture of a second component comprising ,
The proportion of the first component in the whole dielectric ceramic composition is in the range of 30% by weight to 98% by weight , and the proportion of Al 2 O 3 in the first component is more than 0% by weight and 80% by weight or less. And
The proportion of the second component in the whole dielectric ceramic composition is in the range of 2% by weight to 70% by weight, and the proportion of each composition of the second component in the whole second component is 30 to 65% by weight. range of SiO 2, in the range of 10 to 35 wt% B 2 O 3, 5~30 wt% of the Al 2 O 3, ZrO 2, and 0-13 wt% of the range of 0-8 wt% (M is at least one element selected from Ca, Sr, and Ba).
[0009]
[Action]
According to the first dielectric ceramic composition of the present invention, Ca ｛(Mg 1/3 Nb 2/3 ) 1-X Ti having a high relative dielectric constant and excellent microwave dielectric properties as the first component. Since X ｝ O 3 (where 0 ≦ x ≦ 0.50) and the second component contains a glass component that promotes sintering, it is sintered at about 1000 ° C. and has a high relative dielectric constant. A dielectric ceramic having a high Q value and a temperature coefficient of a small resonance frequency can be realized. In addition, since the first component does not contain Bi 2 O 3 , the stability of the dielectric properties with respect to the firing temperature is excellent.
[0010]
According to the second dielectric ceramic composition of the present invention, Ca 本 (Mg 1/3 Nb 2/3 ) 1-x Ti x ｝ O 3 (where 0 ≦ x ≦ 0.50) as the first component ), And by including aluminum oxide having a low relative dielectric constant, the relative dielectric constant can be adjusted without deteriorating the sintering temperature, the Q value, and the temperature coefficient. In addition, since a vitreous component having a lowered melting point is added to the second component, it is sintered at about 1000 ° C., and a dielectric ceramic having a high relative dielectric constant, a high Q value, and a temperature coefficient of a small resonance frequency can be realized. .
[0011]
Further, according to the first and second dielectric porcelain compositions of the present invention, the second component is SiO 2 in the range of 30 to 65% by weight, B 2 O 3 in the range of 10 to 35% by weight, in the range of 30 wt% Al 2 O 3, ZrO 2 in the range of 0-8 wt%, and 0-13 wt% of the MO (M is at least one element selected Ca, Sr, from Ba) since consisting further enables low-temperature sintering can be realized a high dielectric constant, high Qf product, a dielectric ceramic composition having a microwave dielectric properties and excellent temperature coefficient of small resonant frequencies.
[0012]
In the above, the relative dielectric constant (ε r ) of the dielectric ceramic composition is in the range of 14 to 40, the Qf product is in the range of 1000 to 30,000 GHz, and the temperature coefficient of resonance frequency (τ f ) is in the range of −50 to +50 ppm / ° C. According to a preferred example, the relative permittivity (ε r ) of the body porcelain composition is 9 to 24, the Qf product is 1000 to 30000 GHz, and the temperature coefficient (τ f ) of the resonance frequency is −50 to +50 ppm / ° C. Thus, a laminated microwave resonance device can be realized, and high-frequency devices such as filters and duplexers can be reduced in size and improved in performance.
[0013]
Further, when the dielectric composition of the present invention is used, a laminated microwave resonance device using Au, Ag, Cu or the like as an internal conductor can be realized, and miniaturization and high performance of high frequency devices such as filters and duplexers can be realized. It becomes possible.
[0014]
【Example】
Hereinafter, the present invention will be described more specifically with reference to examples.
[0015]
(Example 1)
First, the synthesis of the powder used as the first component will be described. The starting materials used were CaCO 3 , MgO, Nb 2 O 5 , and TiO 2 which are chemically highly pure (99% by weight or more). After the purity of the raw material was corrected, the composition was weighed so that x represented by Ca ｛(Mg 1/3 Nb 2/3 ) 1-x Ti x ｝ O 3 became a predetermined value. These powders were mixed with a zirconia ball and pure water in a ball mill for 17 hours. After mixing, the slurry was dried, placed in a crucible made of alumina, and calcined at a temperature of 1000 to 1300 ° C. for 2 hours. After crushing the calcined body, it was crushed with the above-mentioned ball mill for 17 hours and dried to obtain a powder of the first component.
[0016]
Next, the synthesis of the powder used as the second component will be described. Starting materials include SiO 2 , B 2 O 3 , Al 2 O 3 , ZrO 2 , BaCO 3 , SrCO 3 , CaCO 3 , Li 2 O, ZnO, and PbO which are chemically high purity (99% by weight or more). Was used. After correcting the purity of the raw materials, the raw materials were weighed so as to have various compositions shown in Table 1. These powders were mixed in a ball mill using ethanol as a solvent, and dried. The mixed powder was put in a crucible, melted at a temperature of 1000 to 1200 ° C., and rapidly cooled. After pulverization, the mixture was pulverized in the same manner as in mixing and dried to obtain a powder of the second component. Table 1 shows the composition of the synthesized second component.
[0017]
[Table 1]
The powders of the first component and the second component were wet-mixed in a ball mill and dried. 6 wt% of a 5 wt% aqueous solution of polyvinyl alcohol as a binder was added to the obtained powder, mixed, and then granulated through a 32 mesh sieve, and pressed at 100 MPa into a cylindrical shape having a diameter of 13 mm and a thickness of about 5 mm. After the molded body was heated at a temperature of 600 ° C. for 3 hours to incinerate the binder, it was placed in a magnesia porcelain container, covered, and calcined at various temperatures of 800 to 1400 ° C. for 2 hours. The dielectric properties of the sintered body fired at the temperature at which the density was the highest were measured in a microwave. The resonance frequency and the Q value were obtained by a dielectric resonator method. The relative dielectric constant (ε r ) was calculated from the dimensions of the sintered body and the resonance frequency. The resonance frequency was between 4 and 8 GHz. Further, the resonance frequencies at −25 ° C., 20 ° C., and 85 ° C. were measured, and the temperature coefficient (τ f ) was calculated by the least square method. Table 2 shows the results. Here, the Qf product in Table 2 refers to the product of the Q value and the frequency f when the Q value is measured. Here, the frequency f varies between 4 and 8 GHz depending on the size and shape of the material. Therefore, by using the Qf product, the value is calculated as a value that is not affected by the size or shape of the material. This method is a method generally performed by those skilled in the art.
[0019]
[Table 2]
According to Table 2, the porcelain having the composition of this example is sintered at a temperature in the range of 850 to 1150 ° C., has a relative dielectric constant (ε r ) in the range of 14 to 40, a Qf product in the range of 1200 to 18000 GHz, − It was confirmed that it had a temperature coefficient (τ f ) of a resonance frequency of 41 to +48 ppm / ° C. and excellent microwave dielectric properties. Since the composition of the second component can realize excellent dielectric properties even with various compositions as shown in the examples of sample numbers 10 to 13, at least one of SiO 2 and B 2 O 3 is used. It was confirmed that it should be included.
[0021]
As shown in the example of
[0022]
(Example 2)
The synthesis of the sample and the evaluation of the characteristics were performed in the same manner as in Example 1. However, the composition of the second component was as shown in Table 3. Table 4 shows the results.
[0023]
[Table 3]
[Table 4]
From Table 4, dielectric ceramic within the scope of the
[0026]
Example of Sample No. 20 using the second component I having less than 30% by weight of SiO 2 , example of Sample No. 23 using the second component L having more than 35% by weight of B 2 O 3 , and Al 2 O 3 having In the example of sample No. 24 using less than 5% by weight of the second component M, the Qf product is less than 1000 GHz, which is not preferable. Also, the example of sample No. 21 using the second component J in which SiO 2 is more than 65% by weight, the example of sample number 22 using the second component K in which B 2 O 3 is less than 10% by weight, Al 2 O 3 Of the sample No. 25 using the second component N containing more than 30% by weight of ZrO 2 , an example of the sample number 26 using the second component O containing more than 8% by weight of ZrO 2 , and MO (M is Ca, Sr, In the example of Sample No. 27 using the second component P containing at least 13% by weight of one or more selected from Ba), the firing temperature was as high as 1100 ° C. or higher, which was not preferable.
[0027]
(Example 3)
The synthesis of the sample and the evaluation of the characteristics were performed in the same manner as in Example 1. The first component contains Al 2 O 3 in addition to Ca ｛(Mg 1/3 Nb 2/3 ) 1-x Ti x ｝ O 3 . However, the composition of the second component was as shown in Table 1. Table 5 shows the results.
[0028]
[Table 5]
From Table 5, the dielectric porcelain of this example is sintered at a temperature in the range of 850 to 1150 ° C., has a relative dielectric constant (ε r ) in the range of 9 to 24, a Qf product in the range of 1400 to 12000 GHz, and −22. To +46 ppm / ° C. in the resonance frequency temperature coefficient (τ f ) and excellent microwave dielectric properties. The relative dielectric constant could be decreased by increasing the amount W of Al 2 O 3 in the first component.
[0030]
As shown in the example of Sample No. 33, if the amount of the second component is less than 2 % by weight, sintering is not performed at a temperature of 1400 ° C. or less, which is not preferable. As shown in the example of sample No. 38, if the amount of the second component is more than 70% by weight, the Qf product becomes smaller than 1000 GHz, which is not preferable. As shown in the example of sample number 40, when the first components are all Al 2 O 3 , the temperature coefficient of the resonance frequency is undesirably a value negatively greater than −50 ppm / ° C. Further, as shown in the example of sample No. 42, when x in the first component Ca ｛(Mg 1/3 Nb 2/3 ) 1-x Ti x ｝ O 3 exceeds 0.5, the temperature of the resonance frequency becomes The coefficient is a large positive value exceeding +50 ppm / ° C., which is not preferable for practical use.
[0031]
(Example 4)
[0032]
[Table 6]
From Table 6, the dielectric porcelain of this example is sintered at a temperature in the range of 875 to 975 ° C., has a relative dielectric constant (ε r ) in the range of 11 to 24 , a Qf product in the range of 3200 to 5300 GHz, − It was confirmed that it had a temperature coefficient of resonance frequency (τ f ) in the range of 16 to +37 ppm / ° C. and excellent microwave dielectric properties.
[0034]
Example of sample No. 51 using the second component I having less than 30% by weight of SiO 2 , example of sample number 54 using the second component L having more than 35% by weight of B 2 O 3 , and Al 2 O 3 having In the example of Sample No. 55 using less than 5% by weight of the second component M, the Qf product is less than 1000 GHz, which is not preferable. Also, the example of sample number 52 using the second component J in which SiO 2 is more than 65% by weight, the example of sample number 53 using the second component K in which B 2 O 3 is less than 10% by weight, Al 2 O 3 Of Sample No. 56 using the second component N containing more than 30% by weight, sample No. 57 using the second component O containing more than 8% by weight of ZrO 2 , and MO (M is Ca, Sr, In the example of Sample No. 58 using the second component P containing at least 13% by weight of at least one selected from Ba), the firing temperature exceeds 1100 ° C., which is not preferable.
It should be noted that the content of elements other than the above-described examples can be used as long as it does not adversely affect the dielectric properties within the scope of the present invention.
[0035]
(Reference Example 1)
Hereinafter, an example of a laminated resonance device using the dielectric ceramic of the present invention will be described with reference to the drawings. FIG. 1 is a perspective view of a laminated microwave resonance device using a
[0036]
【The invention's effect】
As described above, according to the first dielectric ceramic composition of the present invention, as the first component, Ca ｛(Mg 1/3 Nb 2/3) having a high relative dielectric constant and excellent microwave dielectric properties. 1 ) Since 1-X Ti x ｝ O 3 (where 0 ≦ x ≦ 0.50) and the second component contains a glass component that promotes sintering, sintering is performed at about 1000 ° C. A dielectric ceramic having a high dielectric constant, a high Q value and a temperature coefficient of a small resonance frequency can be realized. In addition, since the first component does not contain Bi 2 O 3 , the stability of the dielectric properties with respect to the firing temperature is excellent.
[0037]
According to the second dielectric ceramic composition of the present invention, Ca 発 明 (Mg 1/3 Nb 2/3 ) 1-x Ti x XO 3 (where 0 ≦ x ≦ 0. In addition to 50), by including aluminum oxide having a low relative dielectric constant, it is possible to adjust the relative dielectric constant without deteriorating the sintering temperature, the Q value, and the temperature coefficient. In addition, since a vitreous component having a lowered melting point is added to the second component, it is sintered at about 1000 ° C., and a dielectric ceramic having a high relative dielectric constant, a high Q value, and a temperature coefficient of a small resonance frequency can be realized. .
[0038]
Further, according to the first and second dielectric ceramic compositions of the present invention, sintering can be performed at a low temperature of about 1000 ° C., and when the relative dielectric constant is as high as about 15 or about 25, a high Q value and a small τ f can be obtained. Can be realized, so that a laminated resonance device using Cu, Au, Ag, or the like for the internal conductor can be realized. This makes it possible to reduce the size and function of high-frequency devices such as filters and duplexers. Further, the dielectric porcelain of the present invention can be used not only for resonance devices, but also for microwave circuit boards, porcelain multilayer capacitors, and the like, and has great industrial value.
[Brief description of the drawings]
FIG. 1 is a perspective view of a laminated microwave resonance device using a dielectric composition according to one embodiment of the present invention.
FIG. 2 is a sectional view taken along line II of FIG.
FIG. 3 is a sectional view taken along line II-II of FIG.
4A is a sectional view taken along line III-III of FIG. 2, FIG. 4B is a sectional view taken along line IV-IV of FIG. 2, and FIG. 4C is a sectional view taken along line VV of FIG. FIG.
[Explanation of symbols]
1
Claims (2)
前記第１成分の誘電体磁器組成物全体に占める割合が４０重量％以上９８重量％以下、
かつ前記第２成分の誘電体磁器組成物全体に占める割合が２重量％以上６０重量％以下の範囲であり、第２成分全体に占める第２成分の各組成の割合が、３０〜６５重量％の範囲のＳｉＯ2、１０〜３５重量％の範囲のＢ2Ｏ3、５〜３０重量％の範囲のＡｌ2Ｏ3、０〜８重量％の範囲のＺｒＯ2、及び０〜１３重量％の範囲のＭＯ（Ｍは、Ｃａ、Ｓｒ、Ｂａから選ばれる少なくとも一種の元素）であることを特徴とする誘電体磁器組成物。A first component represented by the general formula Ca ｛(Mg 1/3 Nb 2/3 ) 1-x Ti x ｝ O 3 (where 0 ≦ x ≦ 0.50) and at least SiO 2 and B 2 O 3 a dielectric ceramic composition comprising a second component comprising a Al 2 O 3 and,
The proportion of the first component in the whole dielectric ceramic composition is 40% by weight or more and 98% by weight or less;
The proportion of the second component in the whole dielectric ceramic composition is in the range of 2% to 60% by weight, and the proportion of each composition of the second component in the whole second component is 30 to 65% by weight. SiO 2 range of 10 to 35 wt% of the B 2 O 3, of from 5 to 30 wt% Al 2 O 3, ZrO 2 in the range of 0-8 wt%, and 0-13 wt% A dielectric porcelain composition characterized by being an MO in the range (M is at least one element selected from Ca, Sr, and Ba).
前記第１成分の誘電体磁器組成物全体に占める割合が３０重量％以上９８重量％以下の範囲であり、第１成分全体に占めるＡｌ 2 Ｏ 3 の割合が０重量％を超え８０重量％以下であり、
かつ第２成分の誘電体磁器組成物全体に占める割合が２重量％以上７０重量％以下の範囲であり、第２成分全体に占める第２成分の各組成の割合が、３０〜６５重量％の範囲のＳｉＯ2、１０〜３５重量％の範囲のＢ2Ｏ3、５〜３０重量％の範囲のＡｌ2Ｏ3、０〜８重量％の範囲のＺｒＯ2、及び０〜１３重量％の範囲のＭＯ（Ｍは、Ｃａ、Ｓｒ、Ｂａから選ばれる少なくとも一種の元素）であることを特徴とする誘電体磁器組成物。Formula Ca {(Mg 1/3 Nb 2/3) 1-x Ti x} O 3 ( however, 0 ≦ x ≦ 0.50) first component consisting of a represented by the composition in Al 2 O 3 Metropolitan And a second component containing at least SiO 2 , B 2 O 3 and Al 2 O 3, and fired by mixing .
The proportion of the first component in the whole dielectric ceramic composition is in the range of 30% by weight to 98% by weight , and the proportion of Al 2 O 3 in the first component is more than 0% by weight and 80% by weight or less. And
The proportion of the second component in the whole dielectric ceramic composition is in the range of 2% by weight to 70% by weight, and the proportion of each composition of the second component in the whole second component is 30 to 65% by weight. range of SiO 2, in the range of 10 to 35 wt% B 2 O 3, 5~30 wt% of the Al 2 O 3, ZrO 2, and 0-13 wt% of the range of 0-8 wt% Wherein M is M (at least one element selected from Ca, Sr, and Ba).
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| JP2848795A JP3597244B2 (en) | 1994-03-08 | 1995-02-16 | Dielectric porcelain composition |
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| JP3704994 | 1994-03-08 | ||
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| JP2848795A JP3597244B2 (en) | 1994-03-08 | 1995-02-16 | Dielectric porcelain composition |
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| JP3597244B2 true JP3597244B2 (en) | 2004-12-02 |
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