JPH0676633A - 誘電体磁器組成物および誘電体共振器 - Google Patents

誘電体磁器組成物および誘電体共振器

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Publication number
JPH0676633A
JPH0676633A JP5115562A JP11556293A JPH0676633A JP H0676633 A JPH0676633 A JP H0676633A JP 5115562 A JP5115562 A JP 5115562A JP 11556293 A JP11556293 A JP 11556293A JP H0676633 A JPH0676633 A JP H0676633A
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Japan
Prior art keywords
dielectric
value
resonator
rare earth
composition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
JP5115562A
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English (en)
Other versions
JP2625074B2 (ja
Inventor
Seiichiro Hirahara
誠一郎 平原
Nobuyoshi Fujikawa
信儀 藤川
Shinichi Enami
信一 榎並
Toyomi Nishi
登代美 西
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kyocera Corp
Original Assignee
Kyocera Corp
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Publication date
Application filed by Kyocera Corp filed Critical Kyocera Corp
Priority to JP5115562A priority Critical patent/JP2625074B2/ja
Priority to US08/082,024 priority patent/US5356844A/en
Publication of JPH0676633A publication Critical patent/JPH0676633A/ja
Application granted granted Critical
Publication of JP2625074B2 publication Critical patent/JP2625074B2/ja
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Abstract

(57)【要約】 【構成】金属元素として希土類元素（Ｌｎ），Ａｌ，Ｃ
ａおよびＴｉを含み、これらの成分をモル比でａＬｎ2
Ｏx ・ｂＡｌ2 Ｏ3 ・ｃＣａＯ・ｄＴｉＯ2 と表した
時、ａ, ｂ, ｃ, ｄおよびｘの値がａ＋ｂ＋ｃ＋ｄ＝
１、０．０５６≦ａ≦０．２１４、０．０５６≦ｂ≦
０．２１４、０．２８６≦ｃ≦０．５００、０．２３０
＜ｄ＜０．４７０、３≦ｘ≦４を満足する誘電体磁器組
成物であり、このような組成を有する誘電体を、一対の
入出力端子間に配置してなる誘電体共振器である。 【効果】高周波において高い誘電率、高いＱ値、及び共
振周波数の温度係数の小さい誘電特性を有しており、高
周波にて使用される共振器あるいは回路基板材料として
の用途に対し満足したものが得られる。

Description

【発明の詳細な説明】
【０００１】
【産業上の利用分野】本発明は、例えば、自動車電話,
コードレステレホン, パーソナル無線機, 衛星放送受信
機に搭載されるマイクロ波領域での共振器や回路基板材
料として適した新規な誘電体磁器組成物および誘電体共
振器に関する。
【０００２】
【従来技術】近年、自動車電話, コードレステレホン,
パーソナル無線機, 衛星放送受信機の実用化に伴ってマ
イクロ波領域での誘電体磁器が広く使用されている。こ
のようなマイクロ波用誘電体磁器は主として共振器に用
いられるが、そこに要求される特性として(1) 誘電体中
では波長が1/εr1/2に短縮されるので、小型化の要求に
対して比誘電率が大きい事、(2) 高周波での誘電損失が
小さいこと、すなわち高Ｑ値であること、(3) 共振周波
数の温度に対する変化が小さいこと、即ち、比誘電率の
温度依存性が小さく且つ安定であること、以上の３特性
が主として挙げられる。
【０００３】従来、この種の誘電体磁器としては、例え
ば、BaO-TiO2系材料，BaO-REO-TiO2( 但し、REO は希土
類元素酸化物) 系材料，MgTiO3- CaTiO3系材料などの酸
化物磁器材料が知られている（例えば、特開昭６１−１
０８０６号公報，特開昭６３−１０００５８号公報，特
開昭６０−１９６０３号公報等参照）。
【０００４】
【発明が解決しようとする問題点】しかし乍ら、BaO-Ti
O2系材料では比誘電率εｒが３７〜４０と高く、Ｑ値は
４００００と大きいが、単一相では共振周波数の温度係
数τｆがゼロのものが得難く、組成変化に対する比誘電
率及び比誘電率の温度依存性の変化も大きいため、高い
比誘電率，低い誘電損失を維持したまま共振周波数の温
度係数τｆを安定に小さく制御することが困難である。
【０００５】また、BaO-REO-TiO2系材料についてはBa0-
Nd2O3-TiO2系あるいはBa0-Sm2O3-Ti02系等が知られてい
るが、これらの系では比誘電率εｒが４０〜６０と非常
に高く、また共振周波数の温度係数τｆがゼロのものも
得られているが、Ｑ値が５０００以下と小さい。
【０００６】さらに、MgTiO3-CaTiO3 系材料ではＱ値が
３００００と大きく、共振周波数の温度係数τｆがゼロ
のものも得られているが、比誘電率εｒが１６〜２５と
小さい。
【０００７】このように、上記のいずれの材料において
も高周波用誘電体材料に要求される前記３特性を共に充
分には満足していない。
【０００８】本発明は上記の欠点に鑑み案出されたもの
で、比誘電率が大きく、高Ｑ値で、比誘電率の温度依存
性が小さく且つ安定である誘電体磁器組成物および誘電
体共振器を提供せんとするものである。
【０００９】
【問題点を解決するための手段】本発明者等は上記問題
に対し、検討を重ねた結果、Ｌｎ2 ＯX ，Ａｌ2 Ｏ3 ，
ＣａＯ，ＴｉＯ2 （Ｌｎは少なくとも１種類以上の希土
類元素であり、３≦ｘ≦４）からなり、これらを特定の
範囲に調整することによって、比誘電率が大きく、高Ｑ
値で、比誘電率の温度依存性が小さく且つ安定である誘
電体磁器組成物が得られることを知見した。
【００１０】即ち、本発明の誘電体磁器組成物は、金属
元素として希土類元素（Ｌｎ），Ａｌ，ＣａおよびＴｉ
を含み、これらの成分をモル比でａＬｎ2 Ｏx ・ｂＡｌ
2 Ｏ3 ・ｃＣａＯ・ｄＴｉＯ2 と表した時、ａ, ｂ,
ｃ, ｄおよびｘの値がａ＋ｂ＋ｃ＋ｄ＝１、０．０５６
≦ａ≦０．２１４、０．０５６≦ｂ≦０．２１４、０．
２８６≦ｃ≦０．５００、０．２３０＜ｄ＜０．４７
０、３≦ｘ≦４を満足するものである。また、本発明の
誘電体共振器は、一対の入出力端子間に誘電体磁器を配
置してなり、電磁界結合により作動する誘電体共振器に
おいて、前記誘電体磁器が、金属元素として希土類元素
（Ｌｎ），Ａｌ，ＣａおよびＴｉを含み、これらの成分
をモル比でａＬｎ2 Ｏx ・ｂＡｌ2 Ｏ3 ・ｃＣａＯ・ｄ
ＴｉＯ2 と表した時、ａ, ｂ, ｃ, ｄおよびｘの値がａ
＋ｂ＋ｃ＋ｄ＝１、０．０５６≦ａ≦０．２１４、０．
０５６≦ｂ≦０．２１４、０．２８６≦ｃ≦０．５０
０、０．２３０＜ｄ＜０．４７０、３≦ｘ≦４を満足す
るものである。
【００１１】本発明の誘電体磁器組成物は、金属元素と
して希土類元素（Ｌｎ），Ａｌ，ＣａおよびＴｉを含む
複合酸化物であるが、これらの組成を上記の範囲に限定
した理由は以下の通りである。
【００１２】即ち、０．０５６≦ａ≦０．２１４とした
のは、０．０５６＞ａの場合はτｆが正に大きくなり、
τｆの絶対値が３０を越えてしまうからであり、ａ＞
０．２１４の場合は比誘電率が低下し、Ｑ値が２０００
０よりも低下するとともに、τｆが負に大きくなり、そ
の絶対値が３０を越えてしまうからである。特に、０．
０７８≦ａ≦０．１１６６が好ましい。
【００１３】また、０．０５６≦ｂ≦０．２１４とした
のは、０．０５６＞ｂの場合はＱ値が２００００よりも
低下し、τｆが正に大きくなり、ｂ＞０．２１４の場合
はＱ値が２００００よりも低下するからである。特に、
０．０７８≦ｂ≦０．１１６６が好ましい。
【００１４】さらに、０．２８６≦ｃ≦０．５００とし
たのは、０．２８６＞ｃの場合はＱ値が２００００より
も低下し、ｃ＞０．５００の場合はτｆが負に大きくな
り、その絶対値が３０を越えてしまうからである。特
に、０．３９０≦ｃ≦０．４７が好ましい。
【００１５】また、０．２３０＜ｄ＜０．４７０とした
のは、０．２３０≧ｄの場合はτｆが負に大きくなり、
ｄ≧０．４７０の場合はＱ値が２００００よりも低下す
るからである。特に、０．３４０≦ｄ≦０．４２２が好
ましい。
【００１６】希土類元素（Ｌｎ）としては、Ｙ，Ｌａ，
Ｃｅ，Ｐｒ，Ｓｍ，Ｅｕ，Ｇｄ，Ｄｙ，Ｅｒ，Ｙｂ，Ｎ
ｄ等があり、これらのなかでもＮｄが最も良い。そし
て、本発明では、希土類元素（Ｌｎ）は２種類以上であ
っても良い。比誘電率の温度依存性の点からは、Ｙ，Ｃ
ｅ，Ｐｒ，Ｓｍ，Ｅｕ，Ｇｄ，Ｄｙ，Ｅｒ，Ｙｂが好ま
しい。
【００１７】また、本発明の誘電体磁器組成物は、前記
組成物を主成分として、これに、ＺｎＯ，ＮｉＯ，Ｓｎ
Ｏ2 ，Ｃｏ3 Ｏ4 ，ＭｎＣＯ3 ，ＺｒＯ2 ，ＷＯ3 ，Ｌ
ｉＣＯ3 ，Ｒｂ2 ＣＯ3 ，Ｓｃ2 Ｏ3 ，Ｖ2 Ｏ5 ，Ｃｕ
Ｏ，ＳｉＯ2 ，ＭｇＣＯ3 ，Ｃｒ2 Ｏ3 ，Ｂ2 Ｏ3 ，Ｇ
ｅＯ2 ，Ｓｂ2 Ｏ5 ，Ｎｂ2 Ｏ5 ，Ｔａ2 Ｏ5 等を添加
しても良い。これらは、その添加成分にもよるが、６重
量％以下の割合で添加することができる。これらの中で
も、特に、Ｎｂ2 Ｏ5 ，Ｔａ2 Ｏ5 を１〜４重量％添加
すると、無添加の場合よりも誘電率が向上するととも
に、温度特性が０に近づくため、性能上優れた誘電体磁
器を得ることができる。
【００１８】本発明の誘電体磁器組成物は、例えば、以
下のようにして作成される。出発原料として、高純度の
希土類酸化物，酸化アルミニウム，酸化チタン，炭酸カ
ルシウムの各粉末を用いて、所望の割合となるように秤
量する。この主成分に対してＮｂ2 Ｏ5 ，Ｔａ2 Ｏ5 ，
ＺｎＯ等の粉末を添加しても良い。そして、この後、純
水を加え、混合原料の平均粒径が１．６μｍ以下となる
まで１０〜３０時間、ジルコニアボール等を使用したミ
ルにより湿式混合・粉砕を行う。この混合物を乾燥後、
１１００〜１３００℃で１〜４時間仮焼し、さらに０．
８〜５重量％のバインダーを加えてから整粒し、得られ
た粉末を所望の成形手段、例えば、金型プレス，冷間静
水圧プレス，押出し成形等により任意の形状に成形後、
１５００〜１７００℃の温度で１〜１０時間大気中にお
いて焼成することにより得られる。
【００１９】また、本発明の誘電体共振器は、例えば、
図１のＴＥモード型共振器は、金属ケース１の両側に入
力端子２および出力端子３を形成し、これらの端子２，
３の間に上記したような組成からなる誘電体磁器４を配
置して構成される。このようなＴＥモード型の誘電体共
振器は、入力端子２からマイクロ波が入力され、マイク
ロ波は誘電体磁器４と自由空間との境界の反射によって
誘電体磁器４内に閉じ込められ、特定の周波数で共振を
起こす。この信号が出力端子３と電磁界結合し、出力さ
れる。また、図示しないが、本発明の誘電体磁器組成物
を、ＴＥＭモードを用いた同軸形共振器やストリップ線
路共振器、ＴＭモードの誘電体磁器共振器、その他の共
振器に適用しても良いことは勿論である。
【００２０】
【作用】本発明の誘電体磁器組成物では、金属元素とし
て希土類元素（Ｌｎ），Ａｌ，ＣａおよびＴｉを含む複
合酸化物であるが、これらを特定の範囲に調整すること
によって、比誘電率が大きく、高Ｑ値で、比誘電率の温
度依存性が小さく且つ安定である誘電体磁器組成物が得
られる。
【００２１】また、上記のような組成からなる誘電体磁
器を使用して、電磁界結合により作動する誘電体共振器
を作製することにより、小型で低損失であり、使用温度
に対して安定した共振周波数を得ることが可能となる。
【００２２】
【実施例】出発原料として高純度の希土類酸化物（Ｎｄ
2 Ｏ3 ），酸化アルミニウム（Ａｌ2 Ｏ3 ），酸化チタ
ン（ＴｉＯ2 ），炭酸カルシウム（ＣａＣＯ3 ）の各粉
末を用いてそれらを表１となるように秤量後、純水を加
え、混合原料の平均粒径が１．６μｍ以下となるまで、
ミルにより約２０時間湿式混合・粉砕を行なった。
【００２３】ミルのボールの種類や他の種々の条件によ
り、ＺｒＯ2 やＳｉＯ2 ，その他の希土類元素の不純物
が１重量％以下含有される場合がある。
【００２４】この混合物を乾燥後、１２００℃で２時間
仮焼し、さらに約１重量％のバインダーを加えてから整
粒し、得られた粉末を約１０００Kg/cm2の圧力で円板状
に成形し、１５００〜１７００℃の温度で２時間大気中
において焼成した。
【００２５】得られた磁器の円板部を平面研磨し、アセ
トン中で超音波洗浄し、１５０℃で１時間乾燥した後、
円柱共振器法により測定周波数３．５〜４．５ＧＨｚで
誘電率, Ｑ値, 共振周波数の温度係数τｆを測定した。
Ｑ値は、マイクロ波誘電体において一般に成立するＱ値
×測定周波数ｆ＝一定の関係から１ＧＨｚでのＱ値に換
算した。共振周波数の温度係数τｆは、−４０℃から＋
８５℃間で共振周波数を測定し、２５℃の時の共振周波
数を基準にして、−４０℃〜２５℃および２５℃〜＋８
５℃の温度係数τｆを算出した。結果を表１に示す。
【００２６】
【表１】
【００２７】表１からも明かなように、本発明により得
られた誘電体は、比誘電率が３０以上、Ｑ値が２０００
０（１ＧＨｚにおいて）以上、τｆが±３０〔ｐｐｍ／
℃〕以内の優れた誘電特性が得られた。一方、本発明の
範囲外の誘電体では、比誘電率, またはＱ値が低いか、
またはτｆの絶対値が３０を越えている。
【００２８】また、本発明者等は、表１の試料Ｎo.７，
８，１０において、Ｎｄ2 Ｏ3 のＮｄを他の希土類元素
と代えて実験を行った。結果を表２に示す。尚、表２に
おいて、試料Ｎo.３３〜５５では、表１の試料Ｎo.８の
ａ，ｂ，ｃ，ｄの値、即ち、ａ，ｂが０．０８８１、
ｃ，ｄが０．４１１９であり、試料Ｎo.５６〜６１で
は、表１の試料Ｎo.７のａ，ｂ，ｃ，ｄの値、即ち、
ａ，ｂが０．１０６１、ｃ，ｄが０．３９３９であり、
試料Ｎo.６２〜６７では、表１の試料Ｎo.１０のａ，
ｂ，ｃ，ｄの値、即ち、ａが０．０９４１、ｂが０．０
９２９、ｃが０．４５８７、ｄが０．３５４３を用い
た。
【００２９】
【表２】
【００３０】この表２より、希土類酸化物としてＮｄ2
Ｏ3 に代えて他の希土類酸化物を用いても、まだ比誘電
率３６以上、Ｑ値が２６０００以上、τｆの絶対値が２
６以内と実用用充分な特性値を有していることが判る。
【００３１】さらに、本発明者等は、表１の試料Ｎo.８
の組成を主成分として、この主成分に対して各種の金属
酸化物を添加する実験を行った。結果を表３，４に示
す。
【００３２】
【表３】
【００３３】
【表４】
【００３４】この表３，４より、希土類酸化物としてＮ
ｄ2 Ｏ3 を配合したものに、所定の金属酸化物を添加す
ると、無添加の場合よりも特性は低下するが、まだ比誘
電率３３以上、Ｑ値が１１０００以上、τｆの絶対値が
１２以内と実用用充分な特性値を有していることが判
る。そして、Ｎｂ2 Ｏ5 ，Ｔａ2 Ｏ5 を４重量％以下添
加した場合には、無添加の場合と比較してＱ値および温
度係数が少々低下するが、比誘電率が大きく向上してい
ることが判る。
【００３５】
【発明の効果】以上、詳述した通り、本発明の誘電体磁
器組成物は、金属元素として希土類元素（Ｌｎ），Ａ
ｌ，ＣａおよびＴｉを含む複合酸化物であるが、これら
を特定の範囲に調整することによって、高周波において
高い誘電率、高いＱ値、及び共振周波数の温度係数の小
さい誘電特性を有することができる。従って、高周波に
て使用される共振器あるいは回路基板材料としての用途
に対し満足したものが得られる。
【図面の簡単な説明】
【図１】本発明の誘電体共振器を示す説明図である。
【符号の説明】
１ 金属ケース ２ 入力端子 ３ 出力端子 ４ 誘電体磁器
フロントページの続き (72)発明者 西 登代美 鹿児島県国分市山下町１番４号 京セラ株 式会社総合研究所内

Claims (2)

    【特許請求の範囲】
  1. 【請求項１】金属元素として希土類元素（Ｌｎ），Ａ
    ｌ，ＣａおよびＴｉを含み、これらの成分をモル比で ａＬｎ2 Ｏx ・ｂＡｌ2 Ｏ3 ・ｃＣａＯ・ｄＴｉＯ2 と表した時、ａ, ｂ, ｃ, ｄおよびｘの値が ａ＋ｂ＋ｃ＋ｄ＝１ ０．０５６≦ａ≦０．２１４ ０．０５６≦ｂ≦０．２１４ ０．２８６≦ｃ≦０．５００ ０．２３０＜ｄ＜０．４７０ ３≦ｘ≦４ を満足することを特徴とする誘電体磁器組成物。
  2. 【請求項２】一対の入出力端子間に誘電体磁器を配置し
    てなり、電磁界結合により作動する誘電体共振器におい
    て、前記誘電体磁器が、金属元素として希土類元素（Ｌ
    ｎ），Ａｌ，ＣａおよびＴｉを含み、これらの成分をモ
    ル比で ａＬｎ2 Ｏx ・ｂＡｌ2 Ｏ3 ・ｃＣａＯ・ｄＴｉＯ2 と表した時、ａ, ｂ, ｃ, ｄおよびｘの値が ａ＋ｂ＋ｃ＋ｄ＝１ ０．０５６≦ａ≦０．２１４ ０．０５６≦ｂ≦０．２１４ ０．２８６≦ｃ≦０．５００ ０．２３０＜ｄ＜０．４７０ ３≦ｘ≦４ を満足することを特徴とする誘電体共振器。
JP5115562A 1992-06-24 1993-05-18 誘電体磁器組成物および誘電体共振器 Expired - Lifetime JP2625074B2 (ja)

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