WO1999062840A1 - Composition ceramique dielectrique hyperfrequence - Google Patents

Composition ceramique dielectrique hyperfrequence Download PDF

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Publication number
WO1999062840A1
WO1999062840A1 PCT/JP1998/002467 JP9802467W WO9962840A1 WO 1999062840 A1 WO1999062840 A1 WO 1999062840A1 JP 9802467 W JP9802467 W JP 9802467W WO 9962840 A1 WO9962840 A1 WO 9962840A1
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composition
nd2o3
dielectric
microwave dielectric
dielectric ceramic
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PCT/JP1998/002467
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English (en)
French (fr)
Inventor
Takeshi Shimada
Keisuke Kageyama
Ryouichi Ando
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Sumitomo Special Metals Co., Ltd.
Ando, Soyoko
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Priority to JP04970897A priority Critical patent/JP3961059B2/ja
Priority to JP9049707A priority patent/JPH10188674A/ja
Application filed by Sumitomo Special Metals Co., Ltd., Ando, Soyoko filed Critical Sumitomo Special Metals Co., Ltd.
Priority to EP98923116A priority patent/EP1120385A4/en
Priority to US09/701,310 priority patent/US6331499B1/en
Priority to PCT/JP1998/002467 priority patent/WO1999062840A1/ja
Publication of WO1999062840A1 publication Critical patent/WO1999062840A1/ja

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    • HELECTRICITY
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    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/02Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances
    • H01B3/12Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances ceramics
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    • C04B35/4688Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates based on barium titanates based on phases other than BaTiO3 perovskite phase containing lead compounds
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    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
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    • C04B2235/32Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
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    • C04B2235/00Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
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    • C04B2235/32Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
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    • C04B2235/658Atmosphere during thermal treatment
    • C04B2235/6583Oxygen containing atmosphere, e.g. with changing oxygen pressures
    • C04B2235/6585Oxygen containing atmosphere, e.g. with changing oxygen pressures at an oxygen percentage above that of air

Definitions

  • the present invention relates to a dielectric resonator material having a characteristic of 20 ppm / ° C and usable for a frequency adjusting rod thereof.
  • cavity resonators and waveguides basically utilize the stability of air or vacuum as a propagation medium for radio waves, and reduce the size of the microphone mouth wave circuit.
  • a propagation medium having a dielectric constant higher than that of air or vacuum and having high stability against temperature and the like as well as air and vacuum.
  • the propagation wavelength of the wave is 1 / 3 ⁇ 4 (however, ⁇ relative permittivity) in the medium, the resonance wavelength is also 1 / V3 ⁇ 4, and miniaturization can be achieved.
  • BaO-Ti0 2 -Ln 2 0 3 based ceramic except added Ln 2 0 3 (iNd20 3 and Pr 6 0 u Cr 2 0 3 to be of) (JP-A-7-169326), the dielectric The ratio ( ⁇ ) has a value of 91 to 93, the Q value is as low as 5700 to 6000, the temperature coefficient of the resonance frequency is 6 to 9 ppm / ° C, and the material of the cavity is a resonance material such as iron or copper. There was a problem that it could not be used for a filter with a large temperature coefficient of frequency.
  • the present invention solves the problems of the conventional microwave dielectric porcelain composition, has excellent relative dielectric constant ( ⁇ ) characteristics, has a high Qf value, and can easily realize the adjustment of the temperature coefficient of the resonance frequency.
  • the purpose of the present invention is to provide a microwave dielectric porcelain composition that is most suitable for a filter having a large temperature coefficient of resonance frequency, such as iron or copper, for the material of the cavity.
  • Ln 2 0 3 was substituted for the by replacing the Eu 2 0 3, and knowledge to be able to provide improved temperature coefficient if of resonance frequency before 10 ⁇ - 20ppm / ° C, and La
  • the material may be sintered in the air, but by sintering in an atmosphere containing 80% or more of oxygen, the material has good characteristics of the Qf value and ⁇ ′′ value, and has a temperature characteristic of frequency. It was found that ⁇ was improved to 82.5 to 92.5, and the present invention was completed.
  • the present invention is a.
  • composition formula is 0.5 ⁇ x ⁇ 0.8, 0.3 ⁇ y ⁇ 0.5, 0 ⁇ z ⁇ 0.4, 0 ⁇ w ⁇ l or 0 ⁇ w ⁇ l, 0 ⁇ 1
  • the X is less than 0.5 It is not preferable because the Q value of the dielectric material decreases, and when it exceeds 0.8, the dielectric constant decreases. Further, when y is less than 0.3, the dielectric constant is lowered, and when y exceeds 0.5, the Q value is lowered, which is not preferable. Further, when z exceeds 0.4, the Q value is remarkably reduced, which is not preferable.
  • Particle size ⁇ following BaO, Sm 2 0 3, Nd 2 0 3, Eu 2 0 3, La 2 0 3, Bi 2 0 3, the Ti0 2 powder, Bae x'iSmi.y ⁇ Nd w-vEuwLn ⁇ y.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Compositions Of Oxide Ceramics (AREA)
  • Inorganic Insulating Materials (AREA)

Description

明細書
マイクロ波誘電体磁器組成物
技術分野
この発明は Ba、 Ti、 Sm、 Nd、 La、 Ce、 Pr、 Biおよび 02からなる主要組成 に E112O3を添加含有させて、 ε=82.5~92.5、 Qf= 6000- 7300GHz, xf= 10~ -20ppm/°Cの特性を有し、 誘電体共振器材料およびその周波数調整棒 に使用できる誘電体磁器組成物に関する。
背景技術
近年、 ニューメディアの発達にともない電子技術分野において、 小型化、 デ ジタル化が急速に進められ、 特に、 衛星通信、 自動車電話、 携帯電話などのマ イク口波を用いた通信技術では、 部品の小型化、 高信頼性が高度に要求されて いる。
従来のマイク口波回路では、 空胴共振器や導波管がフィルターや伝送線路と して用いられていたため、 上記小型化、 高信頼性の障害となっていた。 すなわ ち、 空胴共振器や導波管は、 基本的には電波の伝搬媒体として空気あるいは真 空の安定性を利用しているものであリ、 上記マイク口波回路部分を小型化する には、 空気あるいは真空の誘電率に比べて大きな誘電率を有し、 かつ空気や真 空と同様に温度などに対しては高安定性を有する伝搬媒体を利用すればよく、 この場合、 マイクロ波の伝搬波長は媒体中で、 1/ ¾ (但し επ比誘電率)と なるため、 共振波長も、 1/V¾となり、 小型化が達成できる。
従来のマイク口波誘電体磁器組成物としては、 BaO-Ti02-Nd203-Bi203系セ ラミックス (特開昭 56-102003号)、 BaO-Ti02-Sni203-Ce02-Bi203系セラミツ クス (特開昭 62-187162号)が提案されているが、 これらの材料はマイク口波通 信用誘電体としては Qf値が 4000~6500と低く、 またさまざまなキヤビティー に対し、 周波数の温度特性の調整が容易でない問題があった。 また、 BaO-Ti02-Ln203系セラミックス (但し Ln203(iNd203や Pr60uのも のに Cr203を添加) (特開平 7-169326号)は、 比誘電率 (ε)は 91~93の値を有する 、 Q値が 5700~6000と低く、 共振周波数の温度係数 ifも 6~9ppm/°Cであリ、 キヤビティ一の材質が鉄や銅などの共振周波数の温度係数の大きなフィルタ一 には使用できない問題があつた。
発明の開示
この発明は、 従来のマイクロ波誘電体磁器組成物の問題を解消し、 比誘電率 (ε)特性にすぐれ、 高い Qf値を有し、 共振周波数の温度係数の調整が容易に実 現でき、 キヤビティーの材質が鉄や銅などの共振周波数の温度係数の大きな フィルターに最適なマイクロ波誘電体磁器組成物の提供を目的としている。 発明者らは、 Qf値が高く温度特性の改善向上を図ったマイク口波誘電体磁器 組成物の提供を目的に、 磁器組成物について種々研究した結果、 BaO-Ti02- Nd203-Sm203系セラミックスにおいて、 Nd203の一部を Bi203と置換し、 さ らに Nd203の一部を Ln203(但し Ln = La,Ce,Pr)と置換することにより、
8=88.5-92.5, Qf=6000~7300GHz、 if =3 ~- 10ppm/°Cの特性が得られこ とを知見した。
さらに、 前記の置換した Ln203の一部を Eu203と置換することにより、 共振 周波数の温度係数 ifを 10〜- 20ppm/°Cまでに改善提供できることを知見し、 さ らに、 前記材料を大気中で焼結してもよいが、 酸素 80%以上含有の雰囲気で焼 結することにより、 前記 Qf値や τί"値の良好な特性を備えた上で、 周波数の温度 特性 εが 82.5~92.5に向上することを知見し、 この発明を完成した。
発明を実施するための最良の形態
この発明は、
組成式が、 Ba6-3x-{Smi.y(Ndi.w.vEuwLnv)y.zBiz}8 + 2x'Tii8〇54 (但し Ln = La,Ce,Pr,)で 表され、 組成式の x、 y、 z、 w、 v値が下記値を満足することを特徴とするマイ ク口波誘電体磁器組成物である。
0.5<x<0.8、 0.3<y<0.5、 0<z<0.4、 0<w≤lあるいは 0<w≤l、 0<ν≤1 この発明における組成の限定理由を説明する。 組成式が、
Ba6-3x-{Smi.y(Ndi.w.vEuwLnv)y.zBiz}8 + 2x'Tii8054の誘電体磁器組成物にお いて、 Xが 0.5未満では誘電体の Q値が低下し、 又 0.8を越えると誘電率が低下す るので好ましくない。 また、 yが 0.3未満では誘電率の低下を招来し、 0.5を越 えると Q値の低下するので好ましくない。 さらに、 zが 0.4を越えると Q値が著 しく低下するため好ましくない。
また、 前記組成式において、 w、 Vがともに 0の場合は誘電率が低くなり、 更 に温度特性が負になるため、 Eu添加によっても温度特性をコントロールする ことができないため、 w、 Vが共に 0でない方が好ましく、 少なくとも w、 Vの どちらか一方が正の値であることが好ましい。
この発明の誘電体磁器組成物の特性は ε=82.5〜92.5、 周波数の温度特性は 10〜- 20ppm/°C間で連続して変えることができ、 これによりさまざまな材質 及び大きさの共振キヤビティーに良好な電気特性を供給することができる。 実施例 1
粒度 Ιμπι以下の BaO、 Sm203、 Nd203、 Eu203、 La203、 Bi203、 Ti02粉末 を、 Bae x'iSmi.y^Nd w-vEuwLn^y.zBiJs + 2x'Tii8054組成式で、 x = 0.7、 y = 0.4、 z = 0.1、 v = (0.45、 0.4、 0.35、 0.3、 0.25、 0)、 w = (0.05、 0.1、 0.15、 0.2、 0.25、 0.5)となる如く、 配合混合後、 加圧力 1.5T/cm2にて成形後、 空気中及び 100%O2雰囲気中で 1370°Cにて 3時間焼結して、 誘電体セラミック スを作成し、 4.7GHz帯の共振器として、 表 1に示す特性を得た。
実施例 2 粒度 Ιμπι以下の BaO、 Sm203、 Nd203、 Eu203、 Ce02、 Bi203、 Ti02粉末 を、 実施例 1と同一の組成式で、 x=0.7、 y=0.4、 z=0.1、 v=(0.45、 0.4、 0.35、 0.3、 0)、 w = (0.05、 0.1、 0.15、 0.2、 0.5)となる如く、 配合混合後、 実 施例 1と同一の製造条件にて誘電体セラミックスを作成し、 4.7GHz帯の共振器 として、 表 2に示す特性を得た。
実施例 3
粒度 Ιμπι以下の BaO、 Sm203、 Nd203, Eu203、 Pr2On¾ Bi203、 Ti02粉末 を、 実施例 1と同一の組成式で、 x=0.7、 y = 0.4、 z = 0.1、 v=(0.45、 0.4、 0.35、 0.3、 0)、 w = (0.05、 0.1、 0.15、 0.2、 0.5)となる如く、 配合混合後、 実 施例 1と同一の製造条件にて誘電体セラミックスを作成し、 4.7GHz帯の共振器 として、 表 3に示す特性を得た。
比較例
粒度 Ιμπι以下の BaO、 Sm203, Nd203、 Eu203、 La203、 Bi203、 Ti02粉末 を Bae—^iSm y^Ndi-w-vEuwLnv zBiJs + 2x'Tii8054組成式において x = 0.7、 y = 0.4、 z = 0.1、 v=0、 w = 0の組成になる如く配合混合した後、 実 施例と同一条件にて製造して得られた誘電体セラミックスを作成し、 実施例と 同一の共振器を用いて特性を調査して、 表 1に表す。 又、 前記組成式におい て、 x = 0.7、 y = 0.4、 z = 0、 v= l、 Ln二 Laの組成の誘電体セラミックスを実 施例と同一条件にて作成し、 その特性を表 1に表す。
Figure imgf000007_0001
L9PZ0/S6dT/LDd 0^829/66 O
Figure imgf000008_0001
Figure imgf000008_0002
9
.9M0/86df/13d 0 9/66 O 産業上の利用可能性
BaO-Ti02-Nd203-Sm203系セラミックスにおいて、 Nd203の一部を Bi203 と置換し、 さらに Nd203の一部を Ln203(但し Ln = La,Ce,Pr)と置換することに より、 ε=88.5〜92.5、 Qf= 6000- 7300GHz, xf=3〜- 10ppm/°Cの特性が得 られた。 また、 Ln203の代わりに Eu203にて置換することにより、 ε=85、 Qf= 6000GHz, if= -1.5ppm/°Cの特性を持つ誘電体を得ることができる。 更 に、 前記の 2つの効果を併合することにより、 すなわち置換した Ln203の一部 を Eu203と置換することにより、 ε=82.5~92.5、 Qf= 6000- 7300GHz, xf=10〜- 20ppm Cまでに改善でき、 これによリ種々の材質および大きさの共 振キヤビティ一に良好な電気特性を供給することができる。

Claims

請求の範囲
1. 組成式が、 Bae-Sx'iSnu- iNdi-wEu y-zBizk+sx'Ti^O で表さ れ、 組成式の x、 y、 z、 w値が下記値を満足するマイクロ波誘電体磁器組成 物。
0.5<x<0.8、 0.3 <y<0.5、 0<z<0.4、 0<w≤l,
2. 組成式か、 Ba6_3x'{Smi_y'(Ndi_w_vEuwLnv)y_zBiz}8 + 2x'Tii8054 (但し Ln = La,Ce,Pr)で表され、 組成式の x、 y、 z、 w、 v値が下記値を満足する マイク口波誘電体磁器組成物。
0.5<χ<0.8、 0·3 <ν<0.5、 0<z<0.4、 0<w≤l, 0<ν≤1
PCT/JP1998/002467 1996-11-07 1998-06-04 Composition ceramique dielectrique hyperfrequence WO1999062840A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
JP04970897A JP3961059B2 (ja) 1996-11-07 1997-02-17 マイクロ波誘電体磁器組成物
JP9049707A JPH10188674A (ja) 1996-11-07 1997-02-17 マイクロ波誘電体磁器組成物
EP98923116A EP1120385A4 (en) 1998-06-04 1998-06-04 HYPERFREQUENCY DIELECTRIC CERAMIC COMPOSITION
US09/701,310 US6331499B1 (en) 1998-06-04 1998-06-04 Microwave dielectric ceramic composition
PCT/JP1998/002467 WO1999062840A1 (fr) 1996-11-07 1998-06-04 Composition ceramique dielectrique hyperfrequence

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JP31311296 1996-11-07
PCT/JP1998/002467 WO1999062840A1 (fr) 1996-11-07 1998-06-04 Composition ceramique dielectrique hyperfrequence

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US7907090B2 (en) * 2007-06-07 2011-03-15 Vishay Intertechnology, Inc. Ceramic dielectric formulation for broad band UHF antenna
CN113248253A (zh) * 2021-06-11 2021-08-13 天津大学 一种巨介电常数钛酸锶介质陶瓷及其制备方法

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