JP2004010362A - Dielectric porcelain composition for high frequency wave and its manufacturing method - Google Patents

Dielectric porcelain composition for high frequency wave and its manufacturing method Download PDF

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JP2004010362A
JP2004010362A JP2002161345A JP2002161345A JP2004010362A JP 2004010362 A JP2004010362 A JP 2004010362A JP 2002161345 A JP2002161345 A JP 2002161345A JP 2002161345 A JP2002161345 A JP 2002161345A JP 2004010362 A JP2004010362 A JP 2004010362A
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powder
high frequency
dielectric
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basm
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Shuichi Fukuhara
福原　周一
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Toko Inc
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Toko Inc
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a dielectric porcelain composition for high frequency waves suitable for use in manufacturing an electronic component such as a dielectric resonator or a dielectric filter used in a high frequency band of microwaves or extremely high frequency waves or the like, and its manufacturing method. <P>SOLUTION: The dielectric porcelain composition is composed of a solid solution consisting of the three components of xBaNd<SB>2</SB>Ti<SB>4</SB>O<SB>12</SB>-yBaSm<SB>2</SB>Ti<SB>4</SB>O<SB>12</SB>-zBaBi<SB>2</SB>Ti<SB>4</SB>O<SB>12</SB>using crystal powders of BaNd<SB>2</SB>Ti<SB>4</SB>O<SB>12</SB>, BaSm<SB>2</SB>Ti<SB>4</SB>O<SB>12</SB>and BaBi<SB>2</SB>Ti<SB>4</SB>O<SB>12</SB>, wherein x, y, z are respectively represented in 0≤x≤70.9, 0≤y≤70.9, and 29.1≤z≤34.1(mol%) and satisfy x+y+z=100. <P>COPYRIGHT: (C)2004,JPO

Description

【０００１】
【発明の属する技術分野】
本発明は、マイクロ波、ミリ波などの高周波領域で使用される誘電体共振器や誘電体フィルタ等の電子部品に用いるのに適した高周波用誘電体磁器組成物及びその製造方法に関するものである。
【０００２】
【従来の技術】
近年、情報・通信分野ではマイクロ波、ミリ波といった高周波帯域を使用する電子機器が実用化されつつあり、この様な電子機器に用いられる電子部品もその使用される範囲が高周波領域に広がりつつある。また、マイクロ波回路の集積化に伴って、小型で高性能の誘電体共振器が求められている。この様な誘電体共振器に使用される誘電体磁器組成物には、比誘電率εｒが大きいこと、無負荷Ｑが大きいこと、共振周波数の温度係数τｆが安定していること等が要求されている。
【０００３】
【発明が解決しようとする課題】
従来の誘電体磁器組成物としては、ＢａＯ−ＴｉＯ２−Ｎｄ２Ｏ３−Ｂｉ２Ｏ３系や、ＢａＯ−ＴｉＯ２−Ｓｍ２Ｏ３−Ｎｄ２Ｏ３系の材料が知られている。これらの誘電体磁器組成物は、比誘電率εｒが９０程度で、無負荷Ｑが５０００程度であった。近年、電子機器の軽薄短小化に伴って誘電体共振器や誘電体フィルタ等の寸法をさらに小さくする必要があり、そのためには比誘電率εｒをさらに大きくしなければならなかった。しかしながら、これらの誘電体磁器組成物は、比誘電率εｒを大きくすると、無負荷Ｑが小さくなる傾向があった。そこで、無負荷Ｑが劣化することなく比誘電率εｒを大きくできる誘電体磁器組成物が求められている。
また、従来の誘電体磁器組成物は、酸化物を混合して結晶化させる際、その過程において、高周波領域で使用される誘電体共振器の材料として用いた場合に特性の劣化を引き起こす不安定な結晶構造が生じることがあるという問題があった。
【０００４】
本発明は、無負荷Ｑを劣化させることなく比誘電率εｒを大きくできると共に、共振周波数の温度係数τｆの安定性のよい高周波用誘電体磁器組成物を提供することを目的とする。また、本発明は、比誘電率εｒと無負荷Ｑが劣化することがなく、共振周波数の温度係数τｆが不安定になることのない高周波用誘電体磁器組成物の製造方法を提供することを目的とする。
【０００５】
【課題を解決するための手段】
本発明は、原料の混合の仕方を改善することにより、上記の課題を解決するものである。すなわち、本発明による高周波用誘電体磁器組成物は、ＢａＮｄ２Ｔｉ４Ｏ１２、ＢａＳｍ２Ｔｉ４Ｏ１２及び、ＢａＢｉ２Ｔｉ４Ｏ１２の結晶粉体を用いたｘＢａＮｄ２Ｔｉ４Ｏ１２・ｙＢａＳｍ２Ｔｉ４Ｏ１２・ｚＢａＢｉ２Ｔｉ４Ｏ１２の３成分の固溶体からなり、ｘ、ｙ、ｚをそれぞれ０≦ｘ≦７０．９、０≦ｙ≦７０．９、２９．１≦ｚ≦３４．１（モル％）（ただし、ｘ＋ｙ＋ｚ＝１００）にする。
また、本発明の高周波用誘電体磁器組成物の製造方法は、バリウム、チタン、ネオジウム、サマリウム、ビスマスの酸化物をそれぞれ（Ａ）ＢａＯ・４ＴｉＯ２・Ｎｄ２Ｏ３、（Ｂ）ＢａＯ・４ＴｉＯ２・Ｓｍ２Ｏ３、（Ｃ）ＢａＯ・４ＴｉＯ２・Ｂｉ２Ｏ３で表せる組成になる様に混合した後、これらを粉体状態のまま焼成してそれぞれ（ａ）ＢａＮｄ２Ｔｉ４Ｏ１２、（ｂ）ＢａＳｍ２Ｔｉ４Ｏ１２、（ｃ）ＢａＢｉ２Ｔｉ４Ｏ１２の結晶粉体を形成する工程と、この（ａ）ＢａＮｄ２Ｔｉ４Ｏ１２、（ｂ）ＢａＳｍ２Ｔｉ４Ｏ１２、（ｃ）ＢａＢｉ２Ｔｉ４Ｏ１２の結晶粉体を組成式：ｘＢａＮｄ２Ｔｉ４Ｏ１２・ｙＢａＳｍ２Ｔｉ４Ｏ１２・ｚＢａＢｉ２Ｔｉ４Ｏ１２
（ｘ、ｙ、ｚがそれぞれ０≦ｘ≦７０．９、０≦ｙ≦７０．９、２９．１≦ｚ≦３４．１（モル％）、ただし、ｘ＋ｙ＋ｚ＝１００）になる様に混合し、焼成する工程を備える。
【０００６】
【発明の実施の形態】
本発明に係る高周波用誘電体磁器組成物は、予め、原料の酸化物を結晶化させたＢａＮｄ２Ｔｉ４Ｏ１２、ＢａＳｍ２Ｔｉ４Ｏ１２及び、ＢａＢｉ２Ｔｉ４Ｏ１２の３種類の結晶粉体を、ｘＢａＮｄ２Ｔｉ４Ｏ１２・ｙＢａＳｍ２Ｔｉ４Ｏ１２・ｚＢａＢｉ２Ｔｉ４Ｏ１２
（ｘ、ｙ、ｚがそれぞれ０≦ｘ≦７０．９、０≦ｙ≦７０．９、２９．１≦ｚ≦３４．１（モル％）、ただし、ｘ＋ｙ＋ｚ＝１００）になる様に混合し、焼成するので、焼結する際に所定の結晶構造にスムーズに移行させることができ、従来の様に高周波領域で使用される誘電体共振器の材料として用いた場合に特性の劣化を引き起こす不安定な結晶構造が生じることがない。
【０００７】
【実施例】
以下、本発明の実施例について説明する。
まず、本発明による高周波用誘電体磁器組成物の製造方法について説明する。原料として炭酸バリウム（ＢａＣＯ３）粉末、酸化チタン（ＴｉＯ２）粉末、酸化ネオジウム（Ｎｄ２Ｏ３）粉末をそれぞれＢａＯ・４ＴｉＯ２・Ｎｄ２Ｏ３となる様に秤量（例えば、ＢａＣＯ３を１０モル、ＴｉＯ２を４０モル、Ｎｄ２Ｏ３を１０モル）し、ボールミル等で約１６時間湿式混合した後、混合物の水分を蒸発させて、メッシュを通過させて顆粒状にした。この顆粒状の粉体を空気雰囲気下において１３５０℃で焼結した後、焼結した粉体を乳鉢等で解砕してＢａＮｄ２Ｔｉ４Ｏ１２の結晶粉体を得た。
また、原料として炭酸バリウム（ＢａＣＯ３）粉末、酸化チタン（ＴｉＯ２）粉末、酸化サマリウム（Ｓｍ２Ｏ３）粉末をそれぞれＢａＯ・４ＴｉＯ２・Ｓｍ２Ｏ３となる様に秤量（例えば、ＢａＣＯ３を１０モル、ＴｉＯ２を４０モル、Ｓｍ２Ｏ３を１０モル）し、ボールミル等で約１６時間湿式混合した後、混合物の水分を蒸発させて、メッシュを通過させて顆粒状にした。この顆粒状の粉体を空気雰囲気下において１３５０℃で焼結した後、焼結した粉体を乳鉢等で解砕してＢａＳｍ２Ｔｉ４Ｏ１２の結晶粉体を得た。
さらに、原料として炭酸バリウム（ＢａＣＯ３）粉末、酸化チタン（ＴｉＯ２）粉末、酸化ビスマス（Ｂｉ２Ｏ３）粉末をそれぞれＢａＯ・４ＴｉＯ２・Ｂｉ２Ｏ３となる様に秤量（例えば、ＢａＣＯ３を１０モル、ＴｉＯ２を４０モル、Ｂｉ２Ｏ３を１０モル）し、湿式混合した後、混合物の水分を蒸発させ、メッシュを通過させて顆粒状にした粉体を空気雰囲気下において１０５０℃で焼結し、焼結した粉体を乳鉢等で解砕してＢａＢｉ２Ｔｉ４Ｏ１２の結晶粉体を得た。
次に、このＢａＮｄ２Ｔｉ４Ｏ１２、ＢａＳｍ２Ｔｉ４Ｏ１２及び、ＢａＢｉ２Ｔｉ４Ｏ１２の３種類の結晶粉体を所定の組成となる様に秤量し、ボールミル等で約１６時間湿式混合した後、混合物の水分を蒸発させ、らいかい機で有機バインダーと共に混合均質化し、メッシュを通過させて顆粒状にした。この顆粒状の粉体を成形し、焼成して本発明による材料を得た。
【０００８】
本発明による高周波用誘電体磁器組成物の特性の測定は、この顆粒状の粉体を直径１１ｍｍ、高さ１０ｍｍの円板になる様に成形し、１２８０℃まで脱脂、焼成して評価サンプルを得て行った。この特性の測定は、誘電共振法によって測定し、比誘電率と２〜６ＧＨｚの共振周波数ｆ０における無負荷Ｑを求めた。また、２〜６ＧＨｚの共振周波数における温度依存性については−２５〜８５℃の範囲で測定し、温度係数τｆを求めた。
【０００９】
図１は、ＢａＮｄ２Ｔｉ４Ｏ１２、ＢａＳｍ２Ｔｉ４Ｏ１２及び、ＢａＢｉ２Ｔｉ４Ｏ１２の結晶粉体をｘＢａＮｄ２Ｔｉ４Ｏ１２・ｙＢａＳｍ２Ｔｉ４Ｏ１２・ｚＢａＢｉ２Ｔｉ４Ｏ１２になる様に混合し、焼成したものについて、ＢａＮｄ２Ｔｉ４Ｏ１２の結晶粉体のモル比ｘ、ＢａＳｍ２Ｔｉ４Ｏ１２の結晶粉体のモル比ｙ、ＢａＢｉ２Ｔｉ４Ｏ１２の結晶粉体のモル比ｚを変えたときの特性をまとめた表であり、図２はこれを三元図に表示したものである。
本発明による高周波用誘電体磁器組成物は、ＢａＮｄ２Ｔｉ４Ｏ１２の結晶粉体のモル比ｘが０≦ｘ≦７０．９、ＢａＳｍ２Ｔｉ４Ｏ１２の結晶粉体のモル比ｙが０≦ｙ≦７０．９、ＢａＢｉ２Ｔｉ４Ｏ１２の結晶粉体のモル比ｚが２９．１≦ｚ≦３４．１の範囲（ただし、ｘ＋ｙ＋ｚ＝１００）で、比誘電率εｒを１１１〜１２５にすることができた。また、ＢａＮｄ２Ｔｉ４Ｏ１２の結晶粉体のモル比ｘを３３．２、ＢａＳｍ２Ｔｉ４Ｏ１２の結晶粉体のモル比ｙを３７．７、ＢａＢｉ２Ｔｉ４Ｏ１２の結晶粉体のモル比ｚを２９．１としたところ、比誘電率εｒが１２０、２〜６ＧＨｚの共振周波数ｆ０における無負荷Ｑが２１００、−２５℃の時の温度係数τｆが２９．２、８５℃の時の温度係数τｆが３５．４となった。さらに、ｘを１３．２、ｙを５５．２、ｚを３１．６としたところ、比誘電率εｒが１１８、ｆ０Ｑが２４００、−２５℃の時の温度係数τｆが１０．４、８５℃の時の温度係数τｆが１４．５となった。また、ｘを４３．２、ｙを２７．７、ｚを２９．１としたところ、比誘電率εｒが１１７、ｆ０Ｑが２４００、−２５℃の時の温度係数τｆが１９．７、８５℃の時の温度係数τｆが２７．１となった。またさらに、ｘを１３．２、ｙを５７．７、ｚを２９．１としたところ、比誘電率εｒが１１６、ｆ０Ｑが２６００、−２５℃の時の温度係数τｆが１．９、８５℃の時の温度係数τｆが１１．６となった。
【００１０】
【発明の効果】
本発明の高周波用誘電体磁器組成物は、ＢａＮｄ２Ｔｉ４Ｏ１２、ＢａＳｍ２Ｔｉ４Ｏ１２及び、ＢａＢｉ２Ｔｉ４Ｏ１２の結晶粉体を用いたｘＢａＮｄ２Ｔｉ４Ｏ１２・ｙＢａＳｍ２Ｔｉ４Ｏ１２・ｚＢａＢｉ２Ｔｉ４Ｏ１２の３成分の固溶体からなり、ｘ、ｙ、ｚがそれぞれ０≦ｘ≦７０．９、０≦ｙ≦７０．９、２９．１≦ｚ≦３４．１（モル％）（ただし、ｘ＋ｙ＋ｚ＝１００）なので、無負荷Ｑを劣化させることなく比誘電率εｒを大きくできると共に、共振周波数の温度係数τｆの安定性を改善することができる。これによって、マイクロ波、ミリ波などの高周波領域で使用される誘電体共振器や誘電体フィルタ等の電子部品に用いるのに適した高周波用誘電体磁器組成物を得られる。
また、本発明の高周波用誘電体磁器組成物の製造方法は、バリウム、チタン、ネオジウム、サマリウム、ビスマスの酸化物をそれぞれ（Ａ）ＢａＯ・４ＴｉＯ２・Ｎｄ２Ｏ３、（Ｂ）ＢａＯ・４ＴｉＯ２・Ｓｍ２Ｏ３、（Ｃ）ＢａＯ・４ＴｉＯ２・Ｂｉ２Ｏ３で表せる組成になる様に混合した後、これらを粉体状態のまま焼成してそれぞれ（ａ）ＢａＮｄ２Ｔｉ４Ｏ１２、（ｂ）ＢａＳｍ２Ｔｉ４Ｏ１２、（ｃ）ＢａＢｉ２Ｔｉ４Ｏ１２の結晶粉体を形成する工程と、この（ａ）ＢａＮｄ２Ｔｉ４Ｏ１２、（ｂ）ＢａＳｍ２Ｔｉ４Ｏ１２、（ｃ）ＢａＢｉ２Ｔｉ４Ｏ１２の結晶粉体を組成式：ｘＢａＮｄ２Ｔｉ４Ｏ１２・ｙＢａＳｍ２Ｔｉ４Ｏ１２・ｚＢａＢｉ２Ｔｉ４Ｏ１２
（ｘ、ｙ、ｚがそれぞれ０≦ｘ≦７０．９、０≦ｙ≦７０．９、２９．１≦ｚ≦３４．１（モル％）、ただし、ｘ＋ｙ＋ｚ＝１００）になる様に混合し、焼成する工程を備えるので、比誘電率εｒと無負荷Ｑが劣化することがなく、かつ、共振周波数の温度係数τｆが不安定になるのを防止できる。
【図面の簡単な説明】
【図１】本発明の高周波用誘電体磁器組成物の特性を説明するための特性の表である。
【図２】本発明の高周波用誘電体磁器組成物の三元図である。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a high-frequency dielectric ceramic composition suitable for use in electronic components such as dielectric resonators and dielectric filters used in high-frequency regions such as microwaves and millimeter waves, and a method for producing the same. .
[0002]
[Prior art]
In recent years, in the information and communication fields, electronic devices using high frequency bands such as microwaves and millimeter waves have been put into practical use, and the range of use of electronic components used in such electronic devices has been expanding to the high frequency range. . Also, with the integration of microwave circuits, a small and high-performance dielectric resonator is required. The dielectric ceramic composition used in such a dielectric resonator is required to have a large relative dielectric constant εr, a large unloaded Q, a stable temperature coefficient τf of the resonance frequency, and the like. ing.
[0003]
[Problems to be solved by the invention]
The conventional dielectric ceramic composition, or BaO-TiO 2 -Nd 2 O 3 -Bi 2 O 3 system, are known materials BaO-TiO 2 -Sm 2 O 3 -Nd 2 O 3 system. These dielectric ceramic compositions had a relative dielectric constant 誘 電 r of about 90 and an unloaded Q of about 5000. In recent years, as electronic devices have become lighter and thinner, it has been necessary to further reduce the dimensions of dielectric resonators, dielectric filters, and the like, and for that purpose, the relative permittivity εr had to be further increased. However, in these dielectric ceramic compositions, when the relative dielectric constant εr is increased, the unloaded Q tends to decrease. Therefore, a dielectric ceramic composition capable of increasing the relative dielectric constant εr without deteriorating the unloaded Q has been demanded.
In addition, when a conventional dielectric ceramic composition is mixed with an oxide and crystallized, in the process, when used as a material for a dielectric resonator used in a high-frequency region, instability causing deterioration of characteristics is caused. There is a problem that a complicated crystal structure may be generated.
[0004]
An object of the present invention is to provide a high-frequency dielectric ceramic composition that can increase the relative dielectric constant εr without deteriorating the no-load Q and has good stability in the temperature coefficient τf of the resonance frequency. Further, the present invention provides a method for producing a high-frequency dielectric ceramic composition in which the relative permittivity εr and the no-load Q do not deteriorate, and the temperature coefficient τf of the resonance frequency does not become unstable. Aim.
[0005]
[Means for Solving the Problems]
The present invention solves the above problems by improving the method of mixing the raw materials. That is, high-frequency dielectric ceramic composition according to the present invention, BaNd 2 Ti 4 O 12, BaSm 2 Ti 4 O 12 and, xBaNd 2 Ti 4 O 12 · yBaSm using crystalline powder BaBi 2 Ti 4 O 12 2 Ti 4 O 12 .zBaBi 2 It consists of a solid solution of three components of Ti 4 O 12 , and x, y, and z are respectively 0 ≦ x ≦ 70.9, 0 ≦ y ≦ 70.9, 29.1 ≦ z ≦ 34 .1 (mol%) (provided that x + y + z = 100).
A method of manufacturing a high frequency dielectric ceramic composition of the present invention, barium, titanium, neodymium, samarium, bismuth oxide, respectively (A) BaO · 4TiO 2 · Nd 2 O 3, (B) BaO · 4TiO After mixing so that the composition can be represented by 2 · Sm 2 O 3 and (C) BaO · 4TiO 2 · Bi 2 O 3 , they are fired in a powder state and (a) BaNd 2 Ti 4 O 12. , (b) BaSm 2 Ti 4 O 12, forming a crystalline powder of (c) BaBi 2 Ti 4 O 12, the (a) BaNd 2 Ti 4 O 12, (b) BaSm 2 Ti 4 O 12 , (C) a crystal powder of BaBi 2 Ti 4 O 12 having the composition formula: xBaNd 2 Ti 4 O 12 .yBaSm 2 Ti 4 O 12 .zBaBi 2 Ti 4 O 12
(X, y, z are respectively 0 ≦ x ≦ 70.9, 0 ≦ y ≦ 70.9, 29.1 ≦ z ≦ 34.1 (mol%), where x + y + z = 100). And a firing step.
[0006]
BEST MODE FOR CARRYING OUT THE INVENTION
High frequency dielectric ceramic composition according to the present invention, in advance, BaNd 2 Ti 4 O 12 to the oxide of the material was crystallized, BaSm 2 Ti 4 O 12 and three crystals of BaBi 2 Ti 4 O 12 powder, xBaNd 2 Ti 4 O 12 · yBaSm 2 Ti 4 O 12 · zBaBi 2 Ti 4 O 12
(X, y, z are respectively 0 ≦ x ≦ 70.9, 0 ≦ y ≦ 70.9, 29.1 ≦ z ≦ 34.1 (mol%), where x + y + z = 100). Since it is fired, it can be smoothly shifted to a predetermined crystal structure during sintering, and when used as a material of a dielectric resonator used in a high-frequency region as in the related art, it does not cause deterioration of characteristics. No stable crystal structure occurs.
[0007]
【Example】
Hereinafter, examples of the present invention will be described.
First, a method for producing a dielectric ceramic composition for high frequencies according to the present invention will be described. Barium carbonate (BaCO 3 ) powder, titanium oxide (TiO 2 ) powder, and neodymium oxide (Nd 2 O 3 ) powder are weighed as raw materials such that BaO.4TiO 2 .Nd 2 O 3 is obtained (for example, BaCO 3 is 10%). Mol, 40 mol of TiO 2 and 10 mol of Nd 2 O 3 ), and wet-mixed with a ball mill or the like for about 16 hours. Then, the water content of the mixture was evaporated and passed through a mesh to form granules. After sintering the granular powder at 1350 ° C. in an air atmosphere, the sintered powder was crushed in a mortar or the like to obtain a crystal powder of BaNd 2 Ti 4 O 12 .
In addition, barium carbonate (BaCO 3 ) powder, titanium oxide (TiO 2 ) powder, and samarium oxide (Sm 2 O 3 ) powder are weighed as raw materials so as to be BaO.4TiO 2 .Sm 2 O 3 (for example, BaCO 3). Was added, 10 mol of TiO 2 and 10 mol of Sm 2 O 3 were mixed by a ball mill or the like for about 16 hours, and then the mixture was evaporated, and the mixture was passed through a mesh to form granules. After sintering the granular powder at 1350 ° C. in an air atmosphere, the sintered powder was crushed in a mortar or the like to obtain a crystal powder of BaSm 2 Ti 4 O 12 .
Further, barium carbonate as the raw material (BaCO 3) powder, titanium oxide (TiO 2) powder, bismuth oxide (Bi 2 O 3) were weighed powder as respectively a BaO · 4TiO 2 · Bi 2 O 3 ( e.g., BaCO 3 , 10 mol of TiO 2 and 10 mol of Bi 2 O 3 ), and after wet mixing, evaporating the water content of the mixture, passing the mixture through a mesh to give a granular powder at 1050 ° C. in an air atmosphere. And the sintered powder was disintegrated in a mortar or the like to obtain a crystal powder of BaBi 2 Ti 4 O 12 .
Next, the three types of crystal powders of BaNd 2 Ti 4 O 12 , BaSm 2 Ti 4 O 12 and BaBi 2 Ti 4 O 12 are weighed so as to have a predetermined composition, and wet weighed by a ball mill or the like for about 16 hours. After mixing, the water content of the mixture was evaporated, mixed and homogenized with an organic binder using a grinder, and passed through a mesh to form granules. This granular powder was molded and calcined to obtain a material according to the present invention.
[0008]
The measurement of the characteristics of the dielectric ceramic composition for a high frequency wave according to the present invention is performed by molding this granular powder into a disk having a diameter of 11 mm and a height of 10 mm, degreased to 1280 ° C., and baked. I got it. This characteristic was measured by the dielectric resonance method, and the relative permittivity and the no-load Q at the resonance frequency f0 of 2 to 6 GHz were obtained. The temperature dependency at the resonance frequency of 2 to 6 GHz was measured in the range of -25 to 85 ° C, and the temperature coefficient τf was obtained.
[0009]
1, BaNd 2 Ti 4 O 12, BaSm 2 Ti 4 O 12 and, BaBi 2 Ti 4 xBaNd 2 the crystal powder of O 12 Ti 4 O 12 · yBaSm 2 Ti 4 O 12 · zBaBi 2 Ti 4 O 12 mixed so as to become, for those sintered, BaNd 2 Ti 4 O 12 molar ratio x of the crystal powder, BaSm 2 Ti 4 O 12 molar ratio y of the crystal powder, crystals of BaBi 2 Ti 4 O 12 FIG. 2 is a table summarizing the characteristics when the molar ratio z of the powder is changed, and FIG. 2 shows this in a ternary diagram.
In the dielectric ceramic composition for high frequency wave according to the present invention, the molar ratio x of the BaNd 2 Ti 4 O 12 crystal powder is 0 ≦ x ≦ 70.9, and the molar ratio y of the BaSm 2 Ti 4 O 12 crystal powder is y. 0 ≦ y ≦ 70.9, the molar ratio z of the crystal powder of BaBi 2 Ti 4 O 12 is in the range of 29.1 ≦ z ≦ 34.1 (where x + y + z = 100), and the relative dielectric constant εr is 111-111. 125. Further, the molar ratio x of the crystal powder BaNd 2 Ti 4 O 12 33.2, BaSm 2 Ti 4 37.7 molar ratio y of the crystal powder of O 12, crystal powder BaBi 2 Ti 4 O 12 Is 29.1, the relative permittivity εr is 120, the no-load Q at the resonance frequency f 0 of 2 to 6 GHz is 2100, the temperature coefficient τf at −25 ° C. is 29.2, 85 ° C. At this time was 35.4. Furthermore, 13.2 x, 55.2 and y, was 31.6 to z, relative dielectric constant εr is 118, f 0 Q is 2400, the temperature coefficient τf at a -25 ° C. 10.4, The temperature coefficient τf at 85 ° C. was 14.5. Further, 43.2 and x, 27.7 and y, was 29.1 to z, relative dielectric constant εr is 117, f 0 Q is 2400, the temperature coefficient τf at a -25 ° C. 19.7, The temperature coefficient τf at 85 ° C. was 27.1. Furthermore, 13.2 x, 57.7 and y, was 29.1 to z, relative dielectric constant εr is 116, f 0 Q 2600, the temperature coefficient τf at a -25 ° C. 1.9 , 85 ° C., the temperature coefficient τf was 11.6.
[0010]
【The invention's effect】
High frequency dielectric ceramic composition of the present invention, BaNd 2 Ti 4 O 12, BaSm 2 Ti 4 O 12 and, xBaNd 2 Ti 4 O 12 · yBaSm 2 Ti with crystal powder of BaBi 2 Ti 4 O 12 4 O 12 · zBaBi 2 Ti 4 O consists 12 ternary solid solution, x, y, z are each 0 ≦ x ≦ 70.9,0 ≦ y ≦ 70.9,29.1 ≦ z ≦ 34.1 (Mol%) (where x + y + z = 100), the relative permittivity εr can be increased without deteriorating the no-load Q, and the stability of the temperature coefficient τf of the resonance frequency can be improved. As a result, a high-frequency dielectric ceramic composition suitable for use in electronic components such as dielectric resonators and dielectric filters used in high-frequency regions such as microwaves and millimeter waves can be obtained.
A method of manufacturing a high frequency dielectric ceramic composition of the present invention, barium, titanium, neodymium, samarium, bismuth oxide, respectively (A) BaO · 4TiO 2 · Nd 2 O 3, (B) BaO · 4TiO After mixing so that the composition can be represented by 2 · Sm 2 O 3 and (C) BaO · 4TiO 2 · Bi 2 O 3 , they are fired in a powder state and (a) BaNd 2 Ti 4 O 12. , (b) BaSm 2 Ti 4 O 12, forming a crystalline powder of (c) BaBi 2 Ti 4 O 12, the (a) BaNd 2 Ti 4 O 12, (b) BaSm 2 Ti 4 O 12 , (C) a crystal powder of BaBi 2 Ti 4 O 12 having the composition formula: xBaNd 2 Ti 4 O 12 .yBaSm 2 Ti 4 O 12 .zBaBi 2 Ti 4 O 12
(X, y, z are respectively 0 ≦ x ≦ 70.9, 0 ≦ y ≦ 70.9, 29.1 ≦ z ≦ 34.1 (mol%), where x + y + z = 100). Since the baking step is provided, the relative permittivity εr and the no-load Q do not deteriorate, and the temperature coefficient τf of the resonance frequency can be prevented from becoming unstable.
[Brief description of the drawings]
FIG. 1 is a table of characteristics for explaining characteristics of a dielectric ceramic composition for high frequency waves of the present invention.
FIG. 2 is a ternary diagram of the dielectric ceramic composition for high frequency wave of the present invention.

Claims (2)

ＢａＮｄ２Ｔｉ４Ｏ１２、ＢａＳｍ２Ｔｉ４Ｏ１２及び、ＢａＢｉ２Ｔｉ４Ｏ１２の結晶粉体を用いたｘＢａＮｄ２Ｔｉ４Ｏ１２・ｙＢａＳｍ２Ｔｉ４Ｏ１２・ｚＢａＢｉ２Ｔｉ４Ｏ１２の３成分の固溶体からなり、ｘ、ｙ、ｚがそれぞれ０≦ｘ≦７０．９、０≦ｙ≦７０．９、２９．１≦ｚ≦３４．１（モル％）（ただし、ｘ＋ｙ＋ｚ＝１００）であることを特徴とする高周波用誘電体磁器組成物。 BaNd 2 Ti 4 O 12, BaSm 2 Ti 4 O 12 and, BaBi 2 Ti 4 xBaNd 2 using crystalline powder O 12 Ti 4 O 12 · yBaSm 2 Ti 4 O 12 · zBaBi 2 Ti 4 3 of O 12 X, y, and z are 0 ≦ x ≦ 70.9, 0 ≦ y ≦ 70.9, 29.1 ≦ z ≦ 34.1 (mol%) (where x + y + z = 100). A dielectric ceramic composition for high frequencies, characterized in that: バリウム、チタン、ネオジウム、サマリウム、ビスマスの酸化物をそれぞれ（Ａ）ＢａＯ・４ＴｉＯ２・Ｎｄ２Ｏ３、（Ｂ）ＢａＯ・４ＴｉＯ２・Ｓｍ２Ｏ３、（Ｃ）ＢａＯ・４ＴｉＯ２・Ｂｉ２Ｏ３で表せる組成になる様に混合した後、これらを粉体状態のまま焼成してそれぞれ（ａ）ＢａＮｄ２Ｔｉ４Ｏ１２、（ｂ）ＢａＳｍ２Ｔｉ４Ｏ１２、（ｃ）ＢａＢｉ２Ｔｉ４Ｏ１２の結晶粉体を形成する工程と、この（ａ）ＢａＮｄ２Ｔｉ４Ｏ１２、（ｂ）ＢａＳｍ２Ｔｉ４Ｏ１２、（ｃ）ＢａＢｉ２Ｔｉ４Ｏ１２の結晶粉体を組成式：ｘＢａＮｄ２Ｔｉ４Ｏ１２・ｙＢａＳｍ２Ｔｉ４Ｏ１２・ｚＢａＢｉ２Ｔｉ４Ｏ１２
（ｘ、ｙ、ｚがそれぞれ０≦ｘ≦７０．９、０≦ｙ≦７０．９、２９．１≦ｚ≦３４．１（モル％）、ただし、ｘ＋ｙ＋ｚ＝１００）になる様に混合し、焼成する工程を備えたことを特徴とする高周波用誘電体磁器組成物の製造方法。Barium, titanium, neodymium, samarium, oxides of bismuth, respectively (A) BaO · 4TiO 2 · Nd 2 O 3, (B) BaO · 4TiO 2 · Sm 2 O 3, (C) BaO · 4TiO 2 · Bi 2 After mixing such that the composition can be represented by O 3 , these are baked in a powder state and (a) BaNd 2 Ti 4 O 12 , (b) BaSm 2 Ti 4 O 12 , (c) BaBi 2 Ti A step of forming a crystal powder of 4 O 12 and a crystal powder of (a) BaNd 2 Ti 4 O 12 , (b) BaSm 2 Ti 4 O 12 , and (c) BaBi 2 Ti 4 O 12 : XBaNd 2 Ti 4 O 12 · yBaSm 2 Ti 4 O 12 · zBaBi 2 Ti 4 O 12
(X, y, z are respectively 0 ≦ x ≦ 70.9, 0 ≦ y ≦ 70.9, 29.1 ≦ z ≦ 34.1 (mol%), where x + y + z = 100). A method for producing a dielectric ceramic composition for high frequencies, comprising a step of firing.
JP2002161345A 2002-06-03 2002-06-03 Dielectric porcelain composition for high frequency wave and its manufacturing method Pending JP2004010362A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006347820A (en) * 2005-06-16 2006-12-28 Ntn Corp Dielectric ceramic and method of manufacturing the same

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006347820A (en) * 2005-06-16 2006-12-28 Ntn Corp Dielectric ceramic and method of manufacturing the same

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