JPH08277161A - Dielectric ceramic composition - Google Patents
Dielectric ceramic compositionInfo
- Publication number
- JPH08277161A JPH08277161A JP8052996A JP5299696A JPH08277161A JP H08277161 A JPH08277161 A JP H08277161A JP 8052996 A JP8052996 A JP 8052996A JP 5299696 A JP5299696 A JP 5299696A JP H08277161 A JPH08277161 A JP H08277161A
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- oxide
- ceramic composition
- dielectric ceramic
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Abstract
Description
【0001】[0001]
【発明の属する技術分野】本発明は、主にマイクロ波帯
域と言われる領域において使用される共振器等を構成す
る高周波用誘電体磁器組成物に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a high frequency dielectric ceramic composition which constitutes a resonator or the like used mainly in a region called a microwave band.
【0002】[0002]
【従来の技術】近年、高周波用誘電体磁器は、自動車電
話、携帯電話、コードレス電話等の無線通信機器の空中
線共用器(デュプレクサ)や電圧制御発振器(VCO)
等に使用される共振器、あるいはCATV用チューナに
使用されるフィルタ等の材料によく用いられている。こ
れらの材料に高誘電率を有する材料を使用することによ
り高周波の波長を真空中のεr -1/2(εr :比誘電率)
の長さに短縮することができるので、高周波の共振条件
となる1波長、1/2波長、あるいは1/4波長(の長
さ)を短くすることができる。従って、この材料を使用
すれば、高周波の共振(現象)を利用して電気信号を処
理する電子(機能)部品の小型化が容易である。2. Description of the Related Art In recent years, high frequency dielectric porcelain has been used in antenna duplexers and voltage controlled oscillators (VCOs) of radio communication equipment such as car phones, mobile phones and cordless phones.
It is often used as a material for resonators used in, for example, filters used in CATV tuners. By using a material with a high dielectric constant for these materials, the high frequency wavelength can be changed to ε r -1/2 (ε r : relative dielectric constant) in vacuum.
The length can be shortened to 1 wavelength, 1/2 wavelength, or 1/4 wavelength (length thereof), which is a resonance condition of high frequency. Therefore, if this material is used, it is easy to miniaturize an electronic (functional) component that processes an electric signal by utilizing high frequency resonance (phenomenon).
【0003】前記高周波用誘電体磁器に要求される特性
としては、(1)誘電体中では高周波の波長がεr -1/2
に短縮されるので、同じ共振周波数ならば比誘電率(ε
r )が大きいほど小型化できる。従って、可能な限り比
誘電率(εr )が大きいこと、(2)高周波帯域での誘
電損失(1/Q)が小さいこと、すなわちQ値が大きい
こと、(3)温度変化による共振周波数の変化率が小さ
いこと、すなわち比誘電率(εr )の温度依存性が小さ
いこと、の3つの特性が挙げられる。The characteristics required for the high-frequency dielectric ceramics are as follows: (1) The high-frequency wavelength is ε r -1/2 in the dielectric.
The relative permittivity (ε
The larger r ), the smaller the size. Therefore, the relative permittivity (ε r ) is as large as possible, (2) the dielectric loss (1 / Q) in the high frequency band is small, that is, the Q value is large, and (3) the resonance frequency of the temperature change. There are three characteristics: a small rate of change, that is, a small temperature dependence of the relative dielectric constant (ε r ).
【0004】また、マイクロ波帯域でも自動車電話、パ
ーソナル無線、コードレステレホン等に用いられる比較
的低周波帯域とされる1GHz程度の領域において適用す
る場合、波長がかなり長くなるため、共振器等の小型化
を図るためには誘電体磁器組成物としては比誘電率(ε
r )がかなり高いものを必要とする。In the microwave band, when it is applied in a region of about 1 GHz, which is a relatively low frequency band used for car telephones, personal radios, cordless telephones, etc., the wavelength becomes considerably long, so that the size of a resonator or the like is small. In order to achieve high dielectric constant, the dielectric ceramic composition must have a relative permittivity (ε
r ) needs something quite high.
【0005】従来、この種の誘電体磁器組成物として
は、例えば、BaOーNd2O3ーTiO2ーBi2O3系組成物、BaOーNd2O
3ーTiO2ーPbO系組成物などが知られている。Conventionally, as this type of dielectric porcelain composition, for example, BaO--Nd 2 O 3 --TiO 2 --Bi 2 O 3 system composition, BaO--Nd 2 O
3 -TiO 2 -PbO-based compositions and the like are known.
【0006】[0006]
【発明が解決しようとする課題】しかしながら、これら
の材料においても比誘電率(εr )は70〜90程度であ
り、それ以上の高い比誘電率(εr )のものを得ようと
すると、急激にQ値が劣化する等、温度特性が劣化し、
比誘電率(εr )を上げ共振器等の小型化を図るには限
度があった。However, even in these materials, the relative permittivity (ε r ) is about 70 to 90, and if an attempt is made to obtain a dielectric constant (ε r ) higher than that, The temperature characteristic deteriorates, such as the Q value suddenly deteriorating.
There has been a limit to increase the relative permittivity (ε r ) and reduce the size of the resonator and the like.
【0007】また、誘電体グリーンシートに内部電極ペ
ーストを印刷してそれらを積層し、その後前記内部電極
ペーストと前記誘電体グリーンシートを同時焼結させ、
この焼結体に外部電極を形成した、いわゆる積層形の誘
電体共振器やフィルタとすることにより、内部導体形状
を色々な形状に設計し、前記焼結体の大きさを共振波長
に比べて大幅に小さくすることも考えられている。In addition, the internal electrode paste is printed on the dielectric green sheet to stack them, and then the internal electrode paste and the dielectric green sheet are simultaneously sintered,
By designing so-called laminated dielectric resonators and filters in which external electrodes are formed on this sintered body, the internal conductor shape is designed in various shapes, and the size of the sintered body is compared with the resonance wavelength. It is also considered to be significantly smaller.
【0008】しかしマイクロ波帯域で使用される電極に
は低抵抗であることが要求されるため、この帯域におけ
る共振器等では一般に電極としてAu、Ag、Cu、Al 等の金属
が使用されており、同時焼結させるにはそれらの金属の
融点よりも低い温度で焼結する組成物が必要になる。However, since electrodes used in the microwave band are required to have low resistance, metals such as Au, Ag, Cu and Al are generally used as electrodes in resonators and the like in this band. However, a composition that sinters at a temperature lower than the melting points of those metals is required for simultaneous sintering.
【0009】しかしながら、従来の高周波用誘電体磁器
は1300〜1500℃で焼結されており、マイクロ波帯域で適
しているAu、Ag、Cu等の金属材料を内部電極材料として採
用することができないといった課題があった。However, the conventional high-frequency dielectric ceramics are sintered at 1300 to 1500 ° C., and metal materials such as Au, Ag, and Cu suitable for the microwave band cannot be adopted as the internal electrode material. There was a problem such as.
【0010】本発明は上記課題に鑑みなされたものであ
り、高周波用共振器等のより一層の小型化を可能とす
る、比誘電率(εr )が高く、誘電損失が低く、比誘電
率(εr )の温度依存性が小さくかつ安定で、従って製
造される誘電体共振器の共振周波数の温度依存性が小さ
く、しかも低融点のAu、Ag-Pd等を内部電極材料として使
用できる低温で焼結可能な誘電体磁器組成物を提供する
ことを目的としている。The present invention has been made in view of the above problems, and has a high relative permittivity (ε r ), a low dielectric loss, and a low relative permittivity, which can further reduce the size of a high frequency resonator or the like. The temperature dependence of (ε r ) is small and stable, so the resonance frequency of the manufactured dielectric resonator is low, and low melting point Au, Ag-Pd, etc. can be used as internal electrode materials. An object of the present invention is to provide a dielectric ceramic composition that can be sintered by.
【0011】[0011]
【課題を解決するための手段及びその効果】本発明者は
上記目的を達成すべく研究を重ねた結果、BaO、Nd2O3、Sm
2O3、TiO2、PbO、Bi2O3からなる系にSiO2、ZnO、B2O3 を添加
することによって、大きな比誘電率(εr )を示し、該
比誘電率(εr )の温度依存性、共振器における共振周
波数の温度依存性が小さく、かつ高Q値の特性を有し、
しかも、Au、AgーPdを内部電極として使用できる1000〜10
50℃の低温で焼結可能な誘電体磁器組成物が得られるこ
とを知見し、本発明を完成するに至った。[Means for Solving the Problem and Its Effect] As a result of repeated studies to achieve the above-mentioned object, the present inventor has found that BaO, Nd 2 O 3, Sm
2 O 3, TiO 2, PbO , SiO 2, ZnO in a system consisting of Bi 2 O 3, by the addition of B 2 O 3, shows a large specific dielectric constant (epsilon r), relative dielectric constant (epsilon r ), The temperature dependence of the resonance frequency in the resonator is small, and has a high Q value,
Moreover, it is possible to use Au and Ag-Pd as internal electrodes.
The inventors have found that a dielectric ceramic composition that can be sintered at a low temperature of 50 ° C. can be obtained, and completed the present invention.
【0012】すなわち、本発明に係る誘電体磁器組成物
は、組成式が xBaO・yNd2O3・zSm2O3・uTiO2・vPbO・wBi2O3 ただし、0.080 <x<0.160 0.121 <y<0.130 0.005 <z<0.030 0.650 <u<0.700 0.045 <v<0.100 0.005 <w<0.045 x+y+z+u+v+w=1 で示される主成分に対し、副成分として SiO2が1.2 〜4.0 重量% ZnO が0.2 〜3.5 重量%及び B2O3が0.1 〜2.5 重量% の割合で添加されていることを特徴としている。Namely, the dielectric ceramic composition according to the present invention, the composition formula xBaO · yNd 2 O 3 · zSm 2 O 3 · uTiO 2 · vPbO · wBi 2 O 3 However, 0.080 <x <0.160 0.121 < y <0.130 0.005 <z <0.030 0.650 <u <0.700 0.045 <v <0.100 0.005 <w <0.045 x + y + z + u + v + w = 1 1.2 to 4.0% by weight of SiO 2 as a minor component ZnO 0.2 to 3.5% by weight % And B 2 O 3 are added in a proportion of 0.1 to 2.5% by weight.
【0013】上記構成の誘電体磁器組成物によれば、比
誘電率(εr )及びQ値が高く、しかも共振周波数の温
度依存性が小さく、さらにはAu、Ag-Pdを内部電極として
使用できる、低温で焼結可能な誘電体磁器組成物を得る
ことができる。According to the dielectric ceramic composition having the above structure, the relative permittivity (ε r ) and the Q value are high, the temperature dependence of the resonance frequency is small, and Au and Ag-Pd are used as the internal electrodes. It is possible to obtain a dielectric ceramic composition that can be sintered at a low temperature.
【0014】従って、高周波用共振器、フィルタ等の大
幅な小型化が可能になり、その有用性は極めて大きい。Therefore, the size of the high-frequency resonator, the filter, etc. can be greatly reduced, and the usefulness thereof is extremely large.
【0015】[0015]
【発明の実施の形態】本発明に係る誘電体磁器組成物
は、主成分としてREO(希土類酸化物)-BaO-TiO2系を基本
としており、希土類酸化物としてNd2O3 とSm2O3 とが用
いられ、それにPbO とBi2O3 とが添加されている。そし
て、1000℃〜1050℃の低温焼結を可能とするため、副成
分として、SiO2、ZnO、B2O3 が添加されている。BEST MODE FOR CARRYING OUT THE INVENTION The dielectric ceramic composition according to the present invention is based on REO (rare earth oxide) -BaO-TiO 2 as a main component, and Nd 2 O 3 and Sm 2 O as rare earth oxides. 3 was used, to which PbO and Bi 2 O 3 were added. Then, in order to enable low temperature sintering at 1000 ° C. to 1050 ° C., SiO 2 , ZnO, and B 2 O 3 are added as auxiliary components.
【0016】各成分が上記範囲を逸脱した場合、1000℃
〜1050℃の低温での焼結が不可能になるか、あるいは可
能な場合でも比誘電率(εr )が低かったり、あるいは
共振周波数の温度係数(τf)が、±20ppm /℃の範囲
を出たり、あるいは、Q値が1500以下と低くなる。When each component deviates from the above range, 1000 ° C.
It becomes impossible to sinter at a temperature as low as ~ 1050 ℃, or even if it is possible, the relative dielectric constant (ε r ) is low, or the temperature coefficient (τf) of the resonance frequency is within ± 20ppm / ℃. It comes out or the Q value becomes as low as 1500 or less.
【0017】[0017]
(I)誘電体磁器の調整 高純度の炭酸バリウム(BaCO3)、酸化ネオジウム(Nd
2O3)、酸化サマリウム(Sm2O3)、酸化チタン(TiO2)、
酸化鉛(PbO)、酸化ビスマス(Bi2O3)、二酸化ケイ素
(SiO2) 、酸化亜鉛(ZnO)、無水ホウ酸(B2O3)をそれ
ぞれ、下記の表1に示した比率で秤量した。(I) Adjustment of dielectric ceramics High-purity barium carbonate (BaCO 3 ), neodymium oxide (Nd)
2 O 3 ), samarium oxide (Sm 2 O 3 ), titanium oxide (TiO 2 ),
Lead oxide (PbO), bismuth oxide (Bi 2 O 3 ), silicon dioxide (SiO 2 ), zinc oxide (ZnO), and boric anhydride (B 2 O 3 ) are weighed in the ratios shown in Table 1 below. did.
【0018】上記出発原料をボールミルにて一昼夜湿
式混合した後乾燥させた。The above starting materials were wet mixed for one day in a ball mill and then dried.
【0019】上記混合物を900 ℃程度の温度で約2時
間仮焼した。The above mixture was calcined at a temperature of about 900 ° C. for about 2 hours.
【0020】仮焼した混合物をボールミルにて一昼夜
湿式粉砕した後乾燥した。The calcined mixture was wet-ground for one day in a ball mill and then dried.
【0021】上記乾燥粉末に約1重量%のバインダを
添加して整粒した。About 1% by weight of a binder was added to the above dry powder to adjust the particle size.
【0022】約1000kg/cm2の圧力で成形し、1000〜13
50℃で約2時間空気中にて焼成した。Molded at a pressure of about 1000 kg / cm 2 , 1000 to 13
It was baked in air at 50 ° C. for about 2 hours.
【0023】(II)特性の測定 得られた誘電体磁器を誘電体円柱共振器法により、共振
周波数3.0 〜4.0GHzにおいて比誘電率(εr )、Q値及
び共振周波数の温度係数(τf)について測定した。(II) Measurement of characteristics The obtained dielectric porcelain was measured by a dielectric cylinder resonator method at a resonance frequency of 3.0 to 4.0 GHz, relative permittivity (ε r ), Q value and temperature coefficient (τf) of resonance frequency. Was measured.
【0024】誘電体磁器組成物の組成、焼結温度、及び
誘電体磁器組成物の特性を下記の表1及び表2に示す。The composition of the dielectric ceramic composition, the sintering temperature, and the characteristics of the dielectric ceramic composition are shown in Tables 1 and 2 below.
【0025】[0025]
【表1】 [Table 1]
【0026】[0026]
【表2】 [Table 2]
【0027】以下、上記表1及び表2に基づき、実施例
のものと比較例のものとを比べ、本発明に係る組成範囲
外での比較例における問題点を述べる。Below, based on Tables 1 and 2, the problems of the comparative examples outside the composition range according to the present invention will be described by comparing the examples and the comparative examples.
【0028】x>0.160 の場合:No.5の様に焼結温度が
1100℃以上必要になり本発明の目的を達成できない。When x> 0.160: As in No. 5, the sintering temperature is
1100 ° C. or higher is required and the object of the present invention cannot be achieved.
【0029】x<0.080 の場合:No.12 の様にQ値が低
くなる。When x <0.080: The Q value becomes low as in No. 12.
【0030】y>0.130 の場合:No.6の様に焼結温度が
1100℃以上必要となる。When y> 0.130: As in No. 6, the sintering temperature is
1100 ° C or higher is required.
【0031】y<0.121 の場合:No.7の様に焼結温度が
1100℃以上になる。When y <0.121: As in No. 7, the sintering temperature is
1100 ℃ or more.
【0032】z>0.030 の場合:No.9の様にτf が負側
に大となる。When z> 0.030: As in No. 9, τf becomes large on the negative side.
【0033】z<0.005 の場合:No.8の様にτf が正側
に大となる。When z <0.005: As in No. 8, τf becomes large on the positive side.
【0034】u>0.700 の場合:No.7の様に焼結温度が
1100℃以上になる。When u> 0.700: As in No. 7, the sintering temperature is
1100 ℃ or more.
【0035】u<0.650 の場合:No.5の様にQ値が低く
なる。When u <0.650: The Q value becomes low as in No. 5.
【0036】v>0.100 の場合:No.12 の様にQ値が低
くなる。When v> 0.100: The Q value becomes low like No.12.
【0037】v<0.045 の場合:No.13 の様にQ値が低
くなる。When v <0.045: The Q value becomes low as in No. 13.
【0038】w>0.045 の場合:No.13 の様にQ値が低
くなる。When w> 0.045: The Q value becomes low as in No. 13.
【0039】w<0.005 の場合:No.15 の様にτf が正
側に大となる。When w <0.005: As in No. 15, τf becomes large on the positive side.
【0040】SiO2>4.0 重量%の場合:No.3の様にεr
が小となる。When SiO 2 > 4.0% by weight: ε r as in No. 3
Is small.
【0041】SiO2<1.2 重量%の場合:No.2、 No.18 、N
o.21の様に焼結温度が1100℃以上になる。When SiO 2 <1.2% by weight: No. 2, No. 18, N
The sintering temperature is 1100 ℃ or higher as in o.21.
【0042】ZnO >3.5 重量%の場合:No.24 の様にQ
値が低くなる。When ZnO> 3.5% by weight: Q as No. 24
The value becomes low.
【0043】ZnO <0.2 重量%の場合:No.19 の様に焼
結温度が1100℃以上になる。When ZnO <0.2% by weight: As in No. 19, the sintering temperature becomes 1100 ° C or higher.
【0044】B2O3>2.5 重量%の場合:No.26 の様にQ
値が低くなる。When B 2 O 3 > 2.5% by weight: Q as No. 26
The value becomes low.
【0045】B2O3<0.1 重量%の場合:No.16 の様に焼
結温度が1100℃以上になる。When B 2 O 3 <0.1% by weight: The sintering temperature becomes 1100 ° C. or higher as shown in No. 16.
【0046】このように比較例のものでは上記のような
問題点が残る。As described above, the above-mentioned problems remain in the comparative example.
【0047】一方、本発明に係る組成の範囲内のもので
ある試料NO.が1、4、10、11、14、17、20、22、23、25 のものに
ついては、いずれも比誘電率(εr )が65.3〜78.2と高
く、Q値もf ×Q=1537〜2650と高く、また、共振周波
数の温度係数(τf)も、 −10.8〜+9.1ppm/ ℃と安定
で、しかも1000〜1050℃で焼結でき、本発明の目的が達
成されている。On the other hand, sample No. 1 within the composition range according to the present invention. , 1, 4, 10, 11, 14, 17, 20, 22, 23, 25 have a high relative dielectric constant (ε r ) of 65.3 to 78.2 and a Q value of f × Q = 1537 to It is as high as 2650, and the temperature coefficient (τf) of the resonance frequency is stable at −10.8 to +9.1 ppm / ° C. and can be sintered at 1000 to 1050 ° C., thus achieving the object of the present invention.
Claims (1)
成物。1. The composition formula is xBaO.yNd 2 O 3 .zSm 2 O 3 .uTiO 2 .vPbO.wBi 2 O 3 where 0.080 <x <0.160 0.121 <y <0.130 0.005 <z <0.030 0.650 <u < 0.700 0.045 <v <0.100 0.005 <w <0.045 x + y + z + u + v + w = 1 to the main component, SiO 2 is 1.2 to 4.0 wt% ZnO is 0.2 to 3.5 wt% and B 2 O 3 is 0.1 to 2.5 wt% % Of the dielectric ceramic composition.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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JP8052996A JPH08277161A (en) | 1996-03-11 | 1996-03-11 | Dielectric ceramic composition |
Applications Claiming Priority (1)
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JP8052996A JPH08277161A (en) | 1996-03-11 | 1996-03-11 | Dielectric ceramic composition |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2090917A Division JPH0717444B2 (en) | 1990-04-04 | 1990-04-04 | Dielectric porcelain composition |
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JPH08277161A true JPH08277161A (en) | 1996-10-22 |
Family
ID=12930547
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JP8052996A Withdrawn JPH08277161A (en) | 1996-03-11 | 1996-03-11 | Dielectric ceramic composition |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6340649B1 (en) | 1999-03-16 | 2002-01-22 | Tdk Corporation | Composition of dielectric ceramics and producing method thereof |
KR100444224B1 (en) * | 2001-11-13 | 2004-08-16 | 삼성전기주식회사 | Dielectric Ceramic Compositions |
-
1996
- 1996-03-11 JP JP8052996A patent/JPH08277161A/en not_active Withdrawn
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6340649B1 (en) | 1999-03-16 | 2002-01-22 | Tdk Corporation | Composition of dielectric ceramics and producing method thereof |
KR100444224B1 (en) * | 2001-11-13 | 2004-08-16 | 삼성전기주식회사 | Dielectric Ceramic Compositions |
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