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KR19990053776A - CaTiO₃ + Ca (Mg⅓ Nb⅔) O₃-based dielectric ceramic composition - Google Patents

CaTiO₃ + Ca (Mg⅓ Nb⅔) O₃-based dielectric ceramic composition Download PDF

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KR19990053776A
KR19990053776A KR1019970073471A KR19970073471A KR19990053776A KR 19990053776 A KR19990053776 A KR 19990053776A KR 1019970073471 A KR1019970073471 A KR 1019970073471A KR 19970073471 A KR19970073471 A KR 19970073471A KR 19990053776 A KR19990053776 A KR 19990053776A
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김경용
최환
박찬식
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박호군
한국과학기술연구원
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G4/00Fixed capacitors; Processes of their manufacture
    • H01G4/002Details
    • H01G4/018Dielectrics
    • H01G4/06Solid dielectrics
    • H01G4/08Inorganic dielectrics
    • H01G4/12Ceramic dielectrics
    • H01G4/1209Ceramic dielectrics characterised by the ceramic dielectric material
    • H01G4/1218Ceramic dielectrics characterised by the ceramic dielectric material based on titanium oxides or titanates
    • H01G4/1227Ceramic dielectrics characterised by the ceramic dielectric material based on titanium oxides or titanates based on alkaline earth titanates
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G4/00Fixed capacitors; Processes of their manufacture
    • H01G4/002Details
    • H01G4/018Dielectrics
    • H01G4/06Solid dielectrics
    • H01G4/08Inorganic dielectrics
    • H01G4/12Ceramic dielectrics
    • H01G4/1209Ceramic dielectrics characterised by the ceramic dielectric material
    • H01G4/1254Ceramic dielectrics characterised by the ceramic dielectric material based on niobium or tungsteen, tantalum oxides or niobates, tantalates

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Abstract

40 이상의 유전율을 갖고 유전 손실이 적으며 공진 주파수의 온도 계수가 양호한 마이크로파용 유전체 세라믹 조성물로서, (1-x)CaTiO3+ xCa(Mg1/3Nb2/3)O3(식 중, 0.4 ≤ x ≤0.7)로 나타내지는 고주파용 유전체 세라믹 조성물을 제공한다. 이 조성물은 필요에 따라 Ca(Mg1/3Nb2/3)O3의 조성비를 달리하여, 유전율과 공진주파수의 온도 계수 조정이 용이하다.A dielectric ceramic composition for microwaves having a dielectric constant of 40 or more, low dielectric loss and good temperature coefficient of resonance frequency, wherein (1-x) CaTiO 3 + xCa (Mg 1/3 Nb 2/3 ) O 3 (wherein 0.4 A dielectric ceramic composition for high frequency represented by ≦ x ≦ 0.7) is provided. This composition varies the composition ratio of Ca (Mg 1/3 Nb 2/3 ) O 3 as needed, and thus it is easy to adjust the temperature coefficient of the dielectric constant and the resonance frequency.

Description

CaTiO₃+Ca(Mg⅓Nb⅔)O₃계 고주파용 유전체 세라믹 조성물High Frequency Dielectric Ceramic Composition for CaTiO₃ + Ca

본 발명은 40∼55의 유전율을 가지며 저손실이고 공진 주파수의 온도 계수가 양호한 마이크로파용 유전체 세라믹 조성물에 관한 것이다.The present invention relates to a dielectric ceramic composition for microwaves having a dielectric constant of 40 to 55, low loss and good temperature coefficient of resonance frequency.

최근 무선 전화기, 자동차 전화기 등의 이동 통신 및 위선 방송, 위성 통신 등에 마이크로파(주파수 대역: 300 MHz부터 30 GHz)를 이용한 통신 시스템이 현저하게 발전하고 있으며, 이러한 뉴미디어의 실용화에 사용되는 공진기, 대역 통과, 저지 필터 및 마이크로파 집적 회로(MIC: Microwave Intergrate Circuit) 등에 고주파용 세라믹 유전체 응용이 크게 증가하였다.Recently, communication systems using microwaves (frequency band: 300 MHz to 30 GHz) for mobile communication, hypocrisy broadcasting, satellite communication of wireless telephones, automobile telephones, etc. have been remarkably developed, and resonators and band pass used in the practical use of new media. Applications of ceramic dielectrics for high frequency applications have increased significantly, for example, stop filters and microwave integrated circuits (MICs).

이러한 고주파용 세라믹 유전체가 통신 시스템에 사용되기 위해서는, 유전체 내에서 전파의 파장은 유전율의 1/2승에 반비례하므로 부품의 소형화를 위해서는 유전율이 커야하고, 유전손실은 유전율에 비례하여 증가하게 되므로 고주파의 고성능화를 위해서는 Q값(유전손실의 역수)이 높아야 한다. 또한 유전체의 공진 주파수의 온도 계수가 작아야 하며 열전도율이 좋고 높은 기계적 강도가 요구된다.In order for the high frequency ceramic dielectric to be used in a communication system, the wavelength of the radio wave in the dielectric is inversely proportional to the power of 1/2 of the dielectric constant. Therefore, the dielectric constant must be large for the miniaturization of components, and the dielectric loss increases in proportion to the dielectric constant. For high performance, the Q value (inverse of the dielectric loss) must be high. In addition, the temperature coefficient of the resonant frequency of the dielectric must be small, and the thermal conductivity is good and high mechanical strength is required.

기존에 개발된 유전체 조성으로는 유전율은 40 이하이지만 낮은 유전 손실을 갖는 Ba(M2+ 1/3M5+ 2/3)O3(M2+= Mg, Zn, M5+= Ta, Nb)계, BaTi4O9와 Ba2Ti9O20계, (Zr,Sn)TiO4계 등이 있다. 또한 유전 손실은 비교적 크지만(Q×f0≤ 10000), 유전율이 80 이상인 BaO-Sm2O3-TiO2계, (Ba,Pb)O-Nd2O3-TiO2계 및 (Pb,Ca)ZrO3계 등이 보고되었다.Existing dielectric compositions include Ba (M 2+ 1/3 M 5+ 2/3 ) O 3 (M 2+ = Mg, Zn, M 5+ = Ta,) Nb), BaTi 4 O 9 and Ba 2 Ti 9 O 20 , and (Zr, Sn) TiO 4 . In addition, although the dielectric loss is relatively large (Q × f 0 ≦ 10000), the BaO—Sm 2 O 3 —TiO 2 system, (Ba, Pb) O—Nd 2 O 3 —TiO 2 system, and (Pb, Ca) ZrO 3 system and the like have been reported.

일반적으로 유전율이 큰 재료는 유전체 내부의 쌍극자와 결함 등으로 인하여 유전 손실과 공진 주파수의 온도 계수가 증가하게 된다.In general, materials with high dielectric constants increase dielectric loss and temperature coefficient of resonance frequency due to dipoles and defects in the dielectric.

CaTiO3의 경우, 2 GHz에서 유전율이 170 정도로 매우 높으나 공진 주파수의 온도 계수가 +800 ppm/℃로 매우 커서 실제 응용에는 문제점이 있다. 따라서 본 발명에서는 CaTiO3에 온도 계수가 음인 Ca(Mg1/3Nb2/3)O3를 고용시켜 유전 손실이 작고, 유전율과 공진 주파수의 온도 계수를 필요에 따라 쉽게 조절할 수 있는 새로운 마이크로파용 유전체 세라믹 조성물을 제공하고자 한다.In the case of CaTiO 3 , the dielectric constant is very high at 170 GHz at 2 GHz, but the temperature coefficient of the resonance frequency is very high at +800 ppm / ° C., which causes problems in practical applications. Therefore, in the present invention, by employing Ca (Mg 1/3 Nb 2/3 ) O 3 having a negative temperature coefficient for CaTiO 3 , the dielectric loss is small, and the new microwave can easily adjust the temperature coefficient of dielectric constant and resonance frequency as needed. SUMMARY To provide a dielectric ceramic composition.

도 1은 본 발명에 의한 유전체 공진기의 조성 변화에 따른 유전 특성을 나타낸 것이고,Figure 1 shows the dielectric properties according to the composition change of the dielectric resonator according to the present invention,

도 2는 본 발명에 의한 유전체 공진기의 조성 변화에 따른 공진 주파수의 온도 계수 특성을 나타낸 것이다.Figure 2 shows the temperature coefficient characteristics of the resonance frequency according to the composition change of the dielectric resonator according to the present invention.

본 발명은 다음 화학식 1을 갖는 조성물을 제조하여, 40∼55의 유전율을 가지며 유전 손실이 작고 공진 주파수의 온도 계수가 양호한 마이크로파용 유전체 세라믹 조성물을 제공한다.The present invention is to prepare a composition having the formula (1), to provide a dielectric ceramic composition for microwave having a dielectric constant of 40 to 55, a low dielectric loss and a good temperature coefficient of the resonance frequency.

(1-x)CaTiO3+ xCa(Mg1/3Nb2/3)O3 (1-x) CaTiO 3 + xCa (Mg 1/3 Nb 2/3 ) O 3

(식 중, 0.4 ≤ x ≤ 0.7)Where 0.4 ≤ x ≤ 0.7

본 발명의 유전체 세라믹 조성물의 특성은 일반식 Ca(Mg1/3Nb2/3)O3의 조성비에 따라 달라진다. 다음 표 1에 나타낸 바와 같이 상기 화학식 1에서의 x 값이 증가하여 Ca(Mg1/3Nb2/3)O3의 함량이 증가함에 따라 유전율은 65∼40의 범위에서 감소하며 공진 주파수의 온도 계수는 상기 화학식 1의 계에서 x 값이 0.625와 0.65 사이에서 +에서 -로 변화됨을 볼 수 있다. 따라서, Ca(Mg1/3Nb2/3)O3의 함량이 0.6∼0.65 mol 부근에서 유전율 44∼47, Q×f0(GHz)가 40000 이상이며 공진 주파수의 온도 계수가 +8∼-3 ppm/℃인 우수한 마이크로파용 유전체 세라믹 조성물을 제조할 수 있다.The properties of the dielectric ceramic composition of the present invention depend on the composition ratio of the general formula Ca (Mg 1/3 Nb 2/3 ) O 3 . As shown in Table 1, the dielectric constant decreases in the range of 65 to 40 and the temperature of the resonant frequency is increased as the content of Ca (Mg 1/3 Nb 2/3 ) O 3 is increased by increasing the x value in Chemical Formula 1 The coefficient can be seen that the x value in the system of Formula 1 is changed from + to-between 0.625 and 0.65. Therefore, when the Ca (Mg 1/3 Nb 2/3 ) O 3 content is 0.6 to 0.65 mol, the dielectric constant is 44 to 47, Q × f 0 (GHz) is 40000 or more and the temperature coefficient of the resonance frequency is +8 to − It is possible to produce excellent microwave dielectric ceramic compositions at 3 ppm / ° C.

한편, 본 조성물은 Ca(Mg1/3Nb2/3)O3의 함량을 조절함에 의해 요구에 맞는 유전율과 공진 주파수의 온도 계수를 자유로이 제어할 수 있는 장점을 갖는다.On the other hand, the present composition has the advantage of freely controlling the temperature coefficient of the dielectric constant and resonant frequency to meet the requirements by adjusting the content of Ca (Mg 1/3 Nb 2/3 ) O 3 .

상기 화학식 1을 갖는 본 발명의 조성물의 제조 방법 및 그 특성의 측정 방법은 다음 실시예를 통해 상세히 설명하고자 한다. 하지만, 본 발명이 이에 한정되는 것은 아니다.The preparation method of the composition of the present invention having the general formula (1) and the method of measuring the properties thereof will be described in detail through the following examples. However, the present invention is not limited thereto.

실시예Example

고순도 화학 연구소의 CaCO3(99.9%), TiO2(99.9%), MgO(99.9%), Nb2O5(99.9%)를 CaTiO3와 Ca(Mg1/3Nb2/3)O3각각의 조성비에 따라 칭량한 후에, 알코올과 지르코니아볼을 매체로 하여 12 시간 동안 습식 혼합하여 건조시킨 후, 1100 ℃에서 3 시간 동안 하소하여 CaTiO3와 Ca(Mg1/3Nb2/3)O3분말을 제조하였다.CaCO 3 (99.9%), TiO 2 (99.9%), MgO (99.9%), and Nb 2 O 5 (99.9%) from the High Purity Chemistry Laboratory, CaTiO 3 and Ca (Mg 1/3 Nb 2/3 ) O 3, respectively. After weighing according to the composition ratio of, the mixture was wet mixed with alcohol and zirconia ball as a medium for 12 hours, dried, and calcined at 1100 ° C. for 3 hours, followed by CaTiO 3 and Ca (Mg 1/3 Nb 2/3 ) O 3. Powder was prepared.

이렇게 하소된 CaTiO3분말과 Ca(Mg1/3Nb2/3)O3분말을 다음 표 1에서와 같은 x 값을 갖는 조성비로 칭량하여, 20 시간 습식 혼합 및 분쇄하였으며, 분쇄 완료 30 분 전에 바인더로서 5% PVA 수용액을 8 중량%로 첨가하였다. 분쇄된 분말을 건조시켜 체거름한 후에 직경이 15 mm인 금속제 주형에서 1 ton/cm2의 압력으로 가압하여 두께가 6 mm 정도인 시편을 성형하였다. 성형된 시편은 박스형 전기로를 이용하여 1550∼1600 ℃ 범위에서 소결하였다. 이때 유기 물질 성분의 제거를 위하여 650 ℃에서 1 시간 동안 유지하였으며 승온과 냉각 속도는 300 ℃/hr이였다.The calcined CaTiO 3 powder and Ca (Mg 1/3 Nb 2/3 ) O 3 powder were weighed at a composition ratio having an x value as shown in Table 1, wet mixed and ground for 20 hours, and 30 minutes before completion of grinding. As a binder, 5% PVA aqueous solution was added at 8% by weight. The pulverized powder was dried, sieved, and pressed into a metal mold having a diameter of 15 mm at a pressure of 1 ton / cm 2 to form a specimen having a thickness of about 6 mm. The molded specimen was sintered in the range of 1550-1600 ° C. using a box-type electric furnace. At this time, it was maintained for 1 hour at 650 ℃ to remove the organic material components and the temperature increase and cooling rate was 300 ℃ / hr.

유전율은 두 장의 은판 사이에서 TE11공진 모드를 이용한 Hakki-Coleman 방법으로 측정하였으며, 같은 지름을 갖고 높이가 3 배인 유전체 2 개를 만들어 TE11과 TE013그리고 은판의 표면 저항을 측정하여 Q 값을 계산하였다. 또한, 25 ℃와 65 ℃에서의 공진 주파수 변화를 측정하여 공진 주파수의 온도 계수를 구하였다. 각 조성별 시편의 마이크로파 유전 특성은 다음 표 1에 나타낸 바와 같다.The dielectric constant was measured by the Hakki-Coleman method using the TE 11 resonance mode between two sheets of silver. Two Q dielectrics of the same diameter and three times the height were made to measure the surface resistances of TE 11 , TE 013 and the silver plate. Calculated. In addition, the temperature coefficient of the resonant frequency was determined by measuring the change in the resonant frequency at 25 ° C and 65 ° C. Microwave dielectric properties of the specimens for each composition are shown in Table 1 below.

(1-x)CaTiO3+ xCa(Mg1/3Nb2/3)O3계 세라믹 조성물의 고주파 유전 특성High Frequency Dielectric Properties of (1-x) CaTiO 3 + xCa (Mg 1/3 Nb 2/3 ) O 3 Based Ceramic Compositions xx 소결 온도Sintering temperature 유전율permittivity Q×f0(GHz)Q × f 0 (GHz) Tf(ppm/℃)T f (ppm / ℃) 0.40.4 1550 ℃/3h1550 ℃ / 3h 64.2364.23 2144421444 81.0381.03 1600 ℃/3h1600 ℃ / 3h 65.1065.10 2230122301 80.6480.64 1600 ℃/20h1600 ℃ / 20h 66.2066.20 2388223882 80.4580.45 0.50.5 1550 ℃/3h1550 ℃ / 3h 54.2654.26 2476424764 34.6734.67 1600 ℃/3h1600 ℃ / 3h 55.0355.03 2577625776 34.3934.39 1600 ℃/20h1600 ℃ / 20h 55.3855.38 2645026450 33.9033.90 0.60.6 1550 ℃/3h1550 ℃ / 3h 44.5944.59 3425234252 8.628.62 1600 ℃/3h1600 ℃ / 3h 45.8445.84 3576835768 8.298.29 1600 ℃/20h1600 ℃ / 20h 47.0947.09 3700637006 8.338.33 0.6250.625 1550 ℃/3h1550 ℃ / 3h 44.4244.42 3571835718 3.503.50 1600 ℃/3h1600 ℃ / 3h 44.8844.88 3821238212 3.473.47 1600 ℃/20h1600 ℃ / 20h 46.0046.00 3917839178 3.353.35 0.650.65 1550 ℃/3h1550 ℃ / 3h 41.9941.99 4112341123 -2.09-2.09 1600 ℃/3h1600 ℃ / 3h 42.1442.14 4164541645 -2.98-2.98 1600 ℃/20h1600 ℃ / 20h 44.1144.11 4261442614 -2.76-2.76 0.70.7 1550 ℃/3h1550 ℃ / 3h 39.5239.52 4505745057 -15.79-15.79 1600 ℃/3h1600 ℃ / 3h 40.3940.39 4604946049 -16.85-16.85 1600 ℃/20h1600 ℃ / 20h 41.5541.55 4841048410 -16.53-16.53

상기 표 1의 결과를 통해 알 수 있는 바와 같이, Ca(Mg1/3Nb2/3)O3을 CaTiO3에 고용시킴으로써, 40 이상의 유전율을 갖고 유전 손실이 작으며 공진 주파수의 온도 계수가 안정한 마이크로파용 유전체 세라믹 조성물을 제조할 수 있으며, 경우에 따라 이 조성비를 달리하여 이 조성물의 유전율과 공진 주파수의 온도 계수를 조절할 수도 있다.As can be seen from the results of Table 1, by dissolving Ca (Mg 1/3 Nb 2/3 ) O 3 in CaTiO 3 , the dielectric constant of 40 or more, the dielectric loss is small and the temperature coefficient of the resonance frequency is stable Microwave dielectric ceramic compositions can be prepared, and in some cases, the composition ratio can be varied to adjust the temperature coefficients of the dielectric constant and resonant frequency of the composition.

Claims (1)

다음 화학식 1을 갖는 고주파용 유전체 세라믹 조성물:A dielectric ceramic composition for high frequency having the formula 화학식 1Formula 1 (1-x)CaTiO3+ xCa(Mg1/3Nb2/3)O3 (1-x) CaTiO 3 + xCa (Mg 1/3 Nb 2/3 ) O 3 (식 중, 0.4 ≤ x ≤ 0.7).Wherein 0.4 ≦ x ≦ 0.7.
KR1019970073471A 1997-12-24 1997-12-24 CATIO₃ + CA (MG⅓NB⅔) O₃ type high frequency dielectric ceramic composition Expired - Fee Related KR100234018B1 (en)

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Publication number Priority date Publication date Assignee Title
JP2001163665A (en) * 1999-12-13 2001-06-19 Murata Mfg Co Ltd Dielectric porcelain composition for high frequency, dielectric resonator, dielectric filter, dielectric duplexer and communication equipment

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KR100339097B1 (en) * 2000-03-16 2002-05-31 장형식 Compositions of Microwave Dielectrics and Production Method thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001163665A (en) * 1999-12-13 2001-06-19 Murata Mfg Co Ltd Dielectric porcelain composition for high frequency, dielectric resonator, dielectric filter, dielectric duplexer and communication equipment

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