KR101271428B1 - Dielectric ceramic compositions for high frequency - Google Patents

Dielectric ceramic compositions for high frequency Download PDF

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KR101271428B1
KR101271428B1 KR1020110127743A KR20110127743A KR101271428B1 KR 101271428 B1 KR101271428 B1 KR 101271428B1 KR 1020110127743 A KR1020110127743 A KR 1020110127743A KR 20110127743 A KR20110127743 A KR 20110127743A KR 101271428 B1 KR101271428 B1 KR 101271428B1
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dielectric
composition
high frequency
temperature
additive
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노승현
강동호
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알에프엠엔씨 주식회사
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/002—Details
    • H01G4/018—Dielectrics
    • H01G4/06—Solid dielectrics
    • H01G4/08—Inorganic dielectrics
    • H01G4/12—Ceramic dielectrics
    • H01G4/1209—Ceramic dielectrics characterised by the ceramic dielectric material
    • H01G4/1254—Ceramic dielectrics characterised by the ceramic dielectric material based on niobium or tungsteen, tantalum oxides or niobates, tantalates
    • H01G4/1263—Ceramic dielectrics characterised by the ceramic dielectric material based on niobium or tungsteen, tantalum oxides or niobates, tantalates containing also zirconium oxides or zirconates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • C01G45/02—Oxides; Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/62605—Treating the starting powders individually or as mixtures
    • C04B35/6261—Milling
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/64—Burning or sintering processes

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  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
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  • Microelectronics & Electronic Packaging (AREA)
  • Inorganic Insulating Materials (AREA)
  • Compositions Of Oxide Ceramics (AREA)

Abstract

PURPOSE: A dielectric ceramic composition for high frequency is provided to control a temperature coefficient of a stable resonance frequency by changing a molar ratio of ANb2O6 and BWO4. CONSTITUTION: A dielectric ceramic compound for high frequency is expressed by a composition formula ZrO2(a)-TiO2(b)-ANb2O6(c)-BWO4(d). In the formula, 0.20<=a<=0.40, 0.50<=b<=0.55, 0.10<=c<=0.30, 0.001<=d<=0.20, A=Zn1-xMgx(0.0<=x<=0.8), and B=Zn, Mg, Ni, Mn, or Co. An additive is added at an amount of 0.1 to 0.3wt% based on a total amount of the composition. The additive is at least one selected from NiO, MnCO3, and Y2O3. The composition is sintered at a temperature of 1200-1300°C. A manufacturing method of the dielectric for high frequency comprises the following steps. ZrO2, TiO2, ANb2O6(A=Zn1-xMgx;0.0<=x<=0.8), and BWO4(B=Zn, Mg, Ni, Mn, Co) are mixed, and the mixture is calcined at a temperature of 900-1100°C in air for 2-4 hours. An additive that is at least one selected from NiO, MnCO3, and Y2O3 is added to the mixture, and the mixture is wet-pulverized. The wet-pulverized mixture is pressure-molded to obtain a mold product. The molded product is sintered at a temperature of 1200-1300°C in air for 3 to 12 hours.

Description

고주파용 유전체 세라믹스 조성물{Dielectric Ceramic Compositions for High Frequency}Dielectric Ceramic Compositions for High Frequency

본 발명은 높은 유전율과 품질계수를 가질 뿐 아니라 조성비를 변화시킴으로써 안정된 공진주파수의 온도조절이 가능한 고주파용 유전체 세라믹스 조성물에 관한 것이다. The present invention relates to a dielectric ceramic composition for high frequency capable of controlling the temperature of a stable resonance frequency by changing the composition ratio as well as having a high dielectric constant and quality coefficient.

정보화 시대가 도래함에 따라 인간이 다루어야 하는 정보의 양은 방대해 졌으며, 정보전달의 중요성도 함께 부각되고 있어서 많은 양의 정보를 시시각각 어디서라도 전달할 수 있는 무선 통신수단의 요구가 급증하고 있다. 이에 따라 이용주파수의 제한을 극복하고 엄청난 수요를 감당하기 위해서는 고주파대역으로의 확장은 필연적이다. 한편 무선통신 분야는 수요의 증가와 더불어 기기의 소형화도 가속화 되고 있다. 이에 따라 우수한 마이크로파 특성을 가진 고주파용 부품 재료를 개발하고자 하는 많은 연구가 진행되고 있다. 최근 유전손실이 낮은 재료의 개발이 중요한 핵심기술로 대두되고 있다. 부품재료의 소형화를 위해서는 유전율이 높아야 하나, 유전율이 높아질수록 손실이 커지는 단점이 있다. 유전체 내부에서 마이크로파 파장이 유전율에 반비례하기 때문에 유전체의 유전율이 크면 소형화가 가능하므로 유전율이 높아야 한다. 공진주파수가 안정화되기 위해서는 작은 유전손실, 즉 유전체의 Q값이 커야 한다. 또한 유전체 공진기의 활용 범위를 넓히기 위해서는 공진주파수의 온도계수 τf 가 0 ppm/℃에 가까워야 한다.With the advent of the information age, the amount of information that humans have to deal with has grown enormously, and the importance of information delivery is also growing, and the demand for wireless communication means capable of delivering a large amount of information anywhere at any time is rapidly increasing. Accordingly, in order to overcome the limitation of the use frequency and to meet the enormous demand, expansion to the high frequency band is inevitable. On the other hand, the wireless communication field is accelerating the miniaturization of devices as demand increases. Accordingly, many studies have been conducted to develop high frequency component materials having excellent microwave characteristics. Recently, the development of materials with low dielectric loss has emerged as an important core technology. In order to miniaturize the part material, the dielectric constant must be high, but the loss is increased as the dielectric constant is increased. Since the microwave wavelength is inversely proportional to the dielectric constant inside the dielectric, the dielectric constant should be high because the dielectric constant is large. In order for the resonance frequency to stabilize, a small dielectric loss, i.e., the Q value of the dielectric must be large. In addition, in order to extend the application range of the dielectric resonator, the temperature coefficient τf of the resonance frequency should be close to 0 ppm / ° C.

이러한 요구조건을 만족시키는 소재를 개발하기 위해 다양한 유전체조성물이 개발되어 왔다. 대한민국 등록특허 제0784928호에는 (BaYSr1 -Y)TiO3 + X 중량부 Li2CO3 (1≤X≤20, 0.01≤Y≤0.99)로 표현되는 고주파 가변 소자용 후막 유전체 세라믹 조성물을, 1000~1350℃ 범위에서 소결 열처리됨에 의해 형성되는 고주파 가변 소자용 후막 유전체 조성물이 개시되어 있으며, 대한민국 공개특허 제2006-0010618호에는 일반식 Ba(Mg1 /3Nb2 /3)O3-xB2O3-yCuO[BMN-B-Cu]로 표시되고, 조성물 전체에 대한 B2O3 와 CuO의 몰분율은 각각 2.0mol%≤x≤30.0mol% 및 0.5mol%≤y≤30.0mol%의 범위의 값을 가지는 저온소결용 고주파 유전체 조성물이 개시되어 있다. 또한 대한민국 공개특허 제2003-0089840호에는 큰 품질계수(Q값)와 유전율을 가지며 또한 공진 주파수의 온도계수가 우수한, (1-x)(Mg1 /3Ta2 /3)O2-xZrO2 (0≤x≤0.2)로 표시되는 고주파용 유전체 세라믹 조성물이 개시되어 있다.Various dielectric compositions have been developed to develop materials that meet these requirements. Korean Patent No. 0848928 discloses a thick film dielectric ceramic composition for a high frequency variable element represented by (Ba Y Sr 1 -Y ) TiO 3 + X parts by weight Li 2 CO 3 (1 ≦ X ≦ 20, 0.01 ≦ Y ≦ 0.99). in ℃ range and is a thick film dielectric composition for high-frequency-adjustment element formed by initiation As the sintering heat treatment, the Republic of Korea Patent Publication No. 2006-0010618 discloses a general formula Ba (Mg 1/3 Nb 2 /3) O 3 -xB 2 O 3 represented by -yCuO [BMN-B-Cu], the mole fractions of B 2 O 3 and CuO with respect to the whole composition are in the range of 2.0 mol% ≦ x ≦ 30.0 mol% and 0.5 mol% ≦ y ≦ 30.0 mol%, respectively. A high temperature sintering high frequency dielectric composition having a composition is disclosed. In addition, Republic of Korea Patent Publication No. 2003-0089840 discloses a having a large quality factor (Q value) and the dielectric constant also an excellent temperature coefficient of resonance frequency, (1-x) (Mg 1/3 Ta 2/3) O 2 -xZrO 2 ( Disclosed is a high frequency dielectric ceramic composition represented by 0 ≦ x ≦ 0.2).

본 발명자들은 유사한 유전특성을 갖는 기존의 고주파유전체 조성보다 비교적 낮은 소결온도를 가지며, 높은 유전율과 품질계수를 가질 뿐만아니라, 조성비를 변화시킴으로써 안정된 공진주파수의 온도계수 조절이 가능한 유전체 조성물에 관하여 연구하였으며 그 결과 본 발명을 완성하게 되었다.The present inventors have studied a dielectric composition that has a relatively lower sintering temperature than the existing high frequency dielectric compositions having similar dielectric properties, has a high dielectric constant and quality coefficient, and is capable of controlling the temperature coefficient of stable resonance frequency by changing the composition ratio. As a result, the present invention has been completed.

따라서 본 발명은 높은 유전율과 품질계수를 가질 뿐만아니라, 조성비를 변화시킴으로써 안정된 공진주파수의 온도계수 조절이 가능한 유전체 조성물을 제공하는 것을 목적으로 한다.Accordingly, an object of the present invention is to provide a dielectric composition having a high dielectric constant and a quality factor, and capable of controlling a temperature coefficient of stable resonance frequency by changing a composition ratio.

또한 본 발명은 상기 유전체 조성물을 이용한 고주파 유전체의 제조방법을 제공하는 것을 다른 목적으로 한다.
Another object of the present invention is to provide a method of manufacturing a high frequency dielectric using the dielectric composition.

상기 목적을 달성하기 위하여 본 발명에 따르면, 하기의 조성식으로 표시되는 고주파용 유전체 세라믹스 조성물이 제공된다. According to the present invention to achieve the above object, there is provided a dielectric ceramic composition for high frequency represented by the following formula.

ZrO2(a)-TiO2(b)-ANb2O6(c)-BWO4(d) ZrO 2 (a) -TiO 2 (b) -ANb 2 O 6 (c) -BWO 4 (d)

[0.20≤a≤0.40, 0.50≤b≤0.55, 0.10≤c≤0.30, 0.001≤d≤0.20이고, A=(Zn1-xMgx;0.0≤x≤0.8), B=Zn, Mg, Ni, Mn 또는 Co임] [0.20 ≦ a ≦ 0.40, 0.50 ≦ b ≦ 0.55, 0.10 ≦ c ≦ 0.30, 0.001 ≦ d ≦ 0.20, A = (Zn 1-x Mg x ; 0.0 ≦ x ≦ 0.8), B = Zn, Mg, Ni , Mn or Co]

소결성을 향상시키기 위하여 상기 조성물에 NiO, MnCO3 및 Y2O3 로 이루어지는 군으로부터 선택되는 적어도 하나를 전체 조성물에 대하여 0.1∼0.3중량%로 첨가하는 것이 바람직하다.NiO, MnCO 3 in the composition to improve the sinterability And at least one selected from the group consisting of Y 2 O 3 is preferably added in an amount of 0.1 to 0.3% by weight based on the total composition.

상기 다른 목적을 달성하기 위하여 본 발명에 따르면, ZrO2, TiO2, ANb2O6(A=Zn1-xMgx;0.0≤x≤0.8), BWO4(B=Zn, Mg, Ni, Mn, Co)를 혼합 후 대기 중에서 900~1100℃의 온도에서 2~4시간 하소하는 단계; NiO, MnCO3 및 Y2O3로 이루어지는 군으로부터 선택되는 적어도 하나의 첨가제를 첨가하여 습식분쇄 하는 단계; 가압성형하여 성형체를 얻는 단계; 및 상기 성형체를 대기 중에서 1200~1300℃의 온도에서 3~12시간 동안 소결하는 단계를 포함하는 고주파용 유전체의 제조방법이 제공된다. 이때 상기 ZrO2, TiO2, ANb2O6(A=Zn1 - xMgx;0.0≤x≤0.8), BWO4(B=Zn, Mg, Ni, Mn, Co)는 0.20~0.40 : 0.50~0.55 : 0.10~0.30 : 0.001~0.20의 비율로 혼합되는 것이 바람직하다. 상기 첨가제는 전체 조성물에 대하여 0.1~0.3중량%의 비율로 첨가되는 것이 바람직하다.
In order to achieve the above another object, according to the present invention, ZrO 2 , TiO 2 , ANb 2 O 6 (A = Zn 1-x Mg x ; 0.0≤x≤0.8) and BWO 4 (B = Zn, Mg, Ni, Mn, Co) after mixing in the air at the temperature of 900 ~ 1100 ℃ 4 hours calcining; NiO, MnCO 3 Wet grinding by adding at least one additive selected from the group consisting of Y 2 O 3 ; Pressing to obtain a molded product; And sintering the molded body for 3 to 12 hours at a temperature of 1200 to 1300 ° C. in the air. At this time, ZrO 2 , TiO 2 , ANb 2 O 6 (A = Zn 1 - x Mg x ; 0.0≤x≤0.8), BWO 4 (B = Zn, Mg, Ni, Mn, Co) is 0.20 to 0.40: 0.50 to 0.55: 0.10 to 0.30: 0.001 It is preferable to mix in the ratio of -0.20. It is preferable that the said additive is added in the ratio of 0.1 to 0.3 weight% with respect to the whole composition.

본 발명에 따라 제조된 유전체 세라믹스 조성물은 높은 유전율과 품질계수를 가질 뿐만 아니라, 조성비를 변화시킴으로써 안정된 공진주파수의 온도계수 조절이 가능하며, 고가의 희토류 물질을 사용하지 않으므로 경제성이 좋다.The dielectric ceramic composition prepared according to the present invention not only has a high dielectric constant and a quality factor, but also can control the temperature coefficient of stable resonance frequency by changing the composition ratio, and it is economical because it does not use expensive rare earth materials.

이하 본 발명을 상세하게 설명한다.Hereinafter, the present invention will be described in detail.

본 발명의 일 실시예에 따르면 하기의 조성식으로 표시되는 고주파용 유전체 세라믹스 조성물이 제공된다. According to an embodiment of the present invention, there is provided a dielectric ceramic composition for high frequency represented by the following compositional formula.

ZrO2(a)-TiO2(b)-ANb2O6(c)-BWO4(d) ZrO 2 (a) -TiO 2 (b) -ANb 2 O 6 (c) -BWO 4 (d)

[0.20≤a≤0.40, 0.50≤b≤0.55, 0.10≤c≤0.30, 0.001≤d≤0.20, a+b+c+d=1 이고, A=(Zn1 - xMgx;0.0≤x≤0.8) B=Zn, Mg, Ni, Mn 또는 Co임] [0.20 ≦ a ≦ 0.40, 0.50 ≦ b ≦ 0.55, 0.10 ≦ c ≦ 0.30, 0.001 ≦ d ≦ 0.20, a + b + c + d = 1, and A = (Zn 1 - x Mg x ; 0.0 ≦ x ≦ 0.8) B = Zn, Mg, Ni, Mn or Co]

본 발명의 상기 유전체 조성물은 큰 값의 유전율(≒40)을 갖는 반면 소결온도가 높고(≒1600℃) 공진주파수의 온도계수가 양으로 큰 값(≒58ppm/℃)을 나타내는 ZrTiO4에 상대적으로 낮은 소결온도(1100~1300℃) 및 큰 품질계수와 음으로 큰 공진주파수의 온도계수를 갖는 ANb2O6(A=Zn1 - xMgx;0.0≤x≤0.8) 와 BWO4(B=Zn, Mg, Ni, Mn, Co)를 동시 치환하여 소결온도 저하 및 유전특성을 개선하는 것에 특징이 있다. 또한 소결성을 향상시키기 위하여 상기 조성물에 NiO, MnCO3 및 Y2O3 로 이루어지는 군으로부터 선택되는 적어도 하나를 전체 조성물에 대하여 0.1∼0.3중량%로 첨가하는 것이 바람직하다.The dielectric composition of the present invention is relatively low in ZrTiO 4 having a high dielectric constant (유전 40) while having a high sintering temperature (≒ 1600 ° C.) and a positive temperature coefficient (≒ 58 ppm / ° C.). ANb 2 O 6 (A = Zn 1 - x Mg x ; 0.0≤x≤0.8) and BWO 4 (B = Zn) with sintering temperature (1100 ~ 1300 ℃), large quality factor and negative temperature coefficient , Mg, Ni, Mn, Co) is characterized in that the sintering temperature is lowered and dielectric properties are improved at the same time. In addition, in order to improve the sinterability, NiO, MnCO 3 And at least one selected from the group consisting of Y 2 O 3 is preferably added in an amount of 0.1 to 0.3% by weight based on the total composition.

상기의 조성물을 이용하여 고주파용 유전체를 제조하는 방법은 다음과 같다.The method for producing a high frequency dielectric using the composition is as follows.

먼저 ZrO2, TiO2, ANb2O6(A=Zn1 - xMgx;0.0≤x≤0.8), BWO4(B=Zn, Mg, Ni, Mn, Co)를 혼합 후 대기 중에서 900~1100℃의 온도에서 2~4시간 하소한다. 여기에 NiO, MnCO3 및 Y2O3로 이루어지는 군으로부터 선택되는 적어도 하나의 첨가제를 첨가하여 습식분쇄 한다. 상기 분쇄물을 가압성형하여 성형체를 얻는다. 상기 성형체를 대기 중에서 1200~1300℃의 온도에서 3~12시간 동안 소결하는 단계를 거쳐 고주파용 유전체를 제조한다. 이때 상기 ZrO2, TiO2, ANb2O6(A=Zn1 - xMgx;0.0≤x≤0.8), BWO4(B=Zn, Mg, Ni, Mn, Co)는 0.20~0.40 : 0.50~0.55 : 0.10~0.30 : 0.001~0.20의 비율로 혼합되는 것이 바람직하다. 상기 첨가제는 전체 조성물에 대하여 0.1~0.3중량%의 비율로 첨가되는 것이 바람직하다.First, ZrO 2 , TiO 2 , ANb 2 O 6 (A = Zn 1 - x Mg x ; 0.0≤x≤0.8) and BWO 4 (B = Zn, Mg, Ni, Mn, Co) after mixing in the air at the temperature of 900 ~ 1100 ℃ 4 hours calcining. At least one additive selected from the group consisting of NiO, MnCO 3 and Y 2 O 3 is added to the wet grinding. The compact is press-molded to obtain a molded body. The molded body is sintered at a temperature of 1200 to 1300 ° C. for 3 to 12 hours in the air to prepare a high frequency dielectric. At this time, ZrO 2 , TiO 2 , ANb 2 O 6 (A = Zn 1 - x Mg x ; 0.0≤x≤0.8), BWO 4 (B = Zn, Mg, Ni, Mn, Co) is 0.20 to 0.40: 0.50 to 0.55: 0.10 to 0.30: 0.001 It is preferable to mix in the ratio of -0.20. It is preferable that the said additive is added in the ratio of 0.1 to 0.3 weight% with respect to the whole composition.

α-PbO2(알파피비오투) 결정구조를 갖는 ZrTiO4에 콜럼바이트(columbite) 결정구조를 갖는 ZnNb2O6 또는 MgNb2O6를 치환시 두 결정구조의 유사성으로 인해 고용체를 형성하여 마이크로파 유전특성 제어가 가능하였다. 또한, ZnNb2O6의 Nb5 +이온 자리에 W6 +이온을 치환시 Ti 이온의 환원(Ti4 +→ Ti3 +)에 의한 품질계수의 저하 개선이 가능하였다. 그리고 저융점의 WO3산화물에 의해 소결온도 저하도 가능하였다.ZnNb 2 O 6 having a columnar crystal structure in ZrTiO 4 having an α-PbO 2 (alphapibiotu) crystal structure Alternatively, the substitution of MgNb 2 O 6 allowed the formation of a solid solution due to the similarity of the two crystal structures to control microwave dielectric properties. In addition, when W 6 + ions were substituted in the Nb 5 + ion sites of ZnNb 2 O 6 , it was possible to improve the reduction of the quality coefficient by reduction of Ti ions (Ti 4 + → Ti 3 + ). In addition, the sintering temperature was also lowered by the low melting point of the WO 3 oxide.

본 발명의 일 실시예에 따른 조성물은 유사한 유전 특성을 갖는 기존의 고주파 유전체 조성 보다 비교적 낮은 소결온도인 1200~1300℃에서 소결이 가능하며, 높은 유전율(Er>40)과 품질계수(Q×F>45,000)를 나타내었다. 나아가 구성성분인 ANb2O6와 BWO4의 몰비를 변화시킴으로써 안정된 공진주파수의 온도계수(+10 ~ -10 ppm/℃)조절이 가능하였다. 또한, 고가의 희토류 물질을 사용하지 않음으로써 비교적 저가에 제조할 수 있는 경쟁력을 갖추고 있다.
The composition according to an embodiment of the present invention is capable of sintering at a relatively low sintering temperature of 1200 ~ 1300 ℃ than conventional high frequency dielectric composition having similar dielectric properties, high dielectric constant (Er> 40) and quality factor (Q × F > 45,000). Furthermore, by changing the molar ratios of ANb 2 O 6 and BWO 4 as constituents, it was possible to control the temperature coefficient (+10 ~ -10 ppm / ℃) of stable resonance frequency. In addition, it does not use expensive rare earth materials, so it has a competitive advantage in manufacturing at a relatively low cost.

이러한 본 발명의 내용을 실시예를 통하여 상세히 설명하고자 한다.
It will be described in detail through the embodiments of the present invention.

[실시예][Example]

출발물질로서 99.9%의 순도를 갖는 ZrO2, TiO2, ZnO, MgO, NiO, CoO, MnO, Nb2O5, WO3, MnCO3 및 Y2O3를 사용하여, 하기의 표 1, 표 2와 같은 조성이 되도록 각 물질들을 정확히 칭량한 후 1차 습식혼합 하였다. 혼합된 분말은 대기 중에서 900~1100℃의 온도에서 3시간 정도 하소한 후 NiO, MnCO3, Y2O3를 첨가하여 2차 습식분쇄 하였다. 분쇄된 분말에 10% PVA수용액 3wt%를 첨가하여 직경 13mm, 두께 5~6mm인 원판형 시편으로 가압 성형하여, 대기 중에서 1200~1300℃의 온도에서 3~12시간 동안 소결하였다.
ZrO 2 , TiO 2 , ZnO, MgO, NiO, CoO, MnO, Nb 2 O 5 , WO 3 , MnCO 3 with 99.9% purity as starting material And using Y 2 O 3 , each material was accurately weighed so as to have a composition as shown in Tables 1 and 2 below, followed by primary wet mixing. The mixed powder was calcined for about 3 hours at the temperature of 900 ~ 1100 ℃ in the air and then secondary wet grinding by adding NiO, MnCO 3 , Y 2 O 3 . 3% by weight of 10% PVA aqueous solution was added to the pulverized powder and pressure-molded into a disk-shaped specimen having a diameter of 13 mm and a thickness of 5 to 6 mm, and then sintered for 3 to 12 hours at an air temperature of 1200 to 1300 ° C.



조성(mol)Composition (mol) 첨가제 (wt%)Additive (wt%) ZrO2(a)
ZrO 2 (a)
TiO2(b)
TiO 2 (b)
(Zn1 - xMgx)Nb2O6(c)(Zn 1 - x Mg x ) Nb 2 O 6 (c) BWO4(d)BWO 4 (d) NiONiO MnCO3 MnCO 3 Y2O3 Y 2 O 3 xx (c)(c) BB (d)(d) 비교예1Comparative Example 1 0.3500 0.3500 0.5000 0.5000 0.0 0.0 0.1500 0.1500 　 　 0.050.05 0.030.03 0.000.00 실시예1Example 1 0.3500 0.3500 0.5000 0.5000 0.0 0.0 0.1250 0.1250 ZnZn 0.0250 0.0250 0.050.05 0.030.03 0.000.00 실시예2Example 2 0.3000 0.3000 0.5000 0.5000 0.0 0.0 0.1750 0.1750 ZnZn 0.0250 0.0250 0.050.05 0.030.03 0.000.00 실시예3Example 3 0.2500 0.2500 0.5000 0.5000 0.0 0.0 0.2250 0.2250 ZnZn 0.0250 0.0250 0.050.05 0.030.03 0.000.00 실시예4Example 4 0.2000 0.2000 0.5000 0.5000 0.0 0.0 0.2750 0.2750 ZnZn 0.0250 0.0250 0.050.05 0.030.03 0.000.00 실시예5Example 5 0.2625 0.2625 0.5000 0.5000 0.2 0.2 0.2313 0.2313 ZnZn 0.0063 0.0063 0.10 0.10 0.030.03 0.05 0.05 실시예6Example 6 0.2612 0.2612 0.5025 0.5025 0.2 0.2 0.2301 0.2301 ZnZn 0.0062 0.0062 0.10 0.10 0.030.03 0.05 0.05 실시예7Example 7 0.2599 0.2599 0.5050 0.5050 0.2 0.2 0.2290 0.2290 ZnZn 0.0062 0.0062 0.10 0.10 0.030.03 0.05 0.05 실시예8Example 8 0.2593 0.2593 0.5062 0.5062 0.2 0.2 0.2284 0.2284 ZnZn 0.0062 0.0062 0.10 0.10 0.030.03 0.05 0.05 실시예9Example 9 0.2586 0.2586 0.5074 0.5074 0.2 0.2 0.2278 0.2278 ZnZn 0.0062 0.0062 0.10 0.10 0.030.03 0.05 0.05 실시예10Example 10 0.2586 0.2586 0.5074 0.5074 0.0 0.0 0.2278 0.2278 ZnZn 0.0062 0.0062 0.10 0.10 0.030.03 0.05 0.05 실시예11Example 11 0.2586 0.2586 0.5074 0.5074 0.1 0.1 0.2278 0.2278 ZnZn 0.0062 0.0062 0.10 0.10 0.030.03 0.05 0.05 실시예12Example 12 0.2586 0.2586 0.5074 0.5074 0.4 0.4 0.2278 0.2278 ZnZn 0.0062 0.0062 0.10 0.10 0.030.03 0.05 0.05 실시예13Example 13 0.2586 0.2586 0.5074 0.5074 0.5 0.5 0.2278 0.2278 ZnZn 0.0062 0.0062 0.10 0.10 0.030.03 0.05 0.05 실시예14Example 14 0.2586 0.2586 0.5074 0.5074 0.8 0.8 0.2278 0.2278 ZnZn 0.0062 0.0062 0.10 0.10 0.030.03 0.05 0.05 실시예15Example 15 0.2600 0.2600 0.5000 0.5000 0.2 0.2 0.2338 0.2338 ZnZn 0.0063 0.0063 0.10 0.10 0.030.03 0.05 0.05 실시예16Example 16 0.2575 0.2575 0.5000 0.5000 0.2 0.2 0.2363 0.2363 ZnZn 0.0063 0.0063 0.10 0.10 0.030.03 0.05 0.05 실시예17Example 17 0.2550 0.2550 0.5000 0.5000 0.2 0.2 0.2388 0.2388 ZnZn 0.0063 0.0063 0.10 0.10 0.030.03 0.05 0.05 실시예18Example 18 0.2525 0.2525 0.5000 0.5000 0.2 0.2 0.2413 0.2413 ZnZn 0.0063 0.0063 0.10 0.10 0.030.03 0.05 0.05 실시예19Example 19 0.2500 0.2500 0.5000 0.5000 0.2 0.2 0.2438 0.2438 ZnZn 0.0063 0.0063 0.10 0.10 0.030.03 0.05 0.05



조성(mol)Composition (mol) 첨가제(wt%)Additive (wt%) ZrO2(a)ZrO 2 (a) TiO2(b)TiO 2 (b) (Zn1 - xMgx)Nb2O6(c)(Zn 1 - x Mg x ) Nb 2 O 6 (c) BWO4(d)BWO 4 (d) NiONiO MnCO3 MnCO 3 Y2O3 Y 2 O 3 xx (c)(c) BB (d)(d) 비교예2Comparative Example 2 0.2625 0.2625 0.5000 0.5000 0.0 0.0 0.2375 0.2375 　 　 0.10 0.10 0.030.03 0.05 0.05 실시예20Example 20 0.2625 0.2625 0.5000 0.5000 0.0 0.0 0.2313 0.2313 ZnZn 0.0063 0.0063 0.10 0.10 0.030.03 0.05 0.05 실시예21Example 21 0.2625 0.2625 0.5000 0.5000 0.0 0.0 0.2250 0.2250 ZnZn 0.0125 0.0125 0.10 0.10 0.030.03 0.05 0.05 실시예22Example 22 0.2625 0.2625 0.5000 0.5000 0.0 0.0 0.2125 0.2125 ZnZn 0.0250 0.0250 0.10 0.10 0.030.03 0.05 0.05 실시예23Example 23 0.2625 0.2625 0.5000 0.5000 0.0 0.0 0.1875 0.1875 ZnZn 0.0500 0.0500 0.10 0.10 0.030.03 0.05 0.05 실시예24Example 24 0.2625 0.2625 0.5000 0.5000 0.0 0.0 0.1375 0.1375 ZnZn 0.1000 0.1000 0.10 0.10 0.030.03 0.05 0.05 실시예25Example 25 0.2625 0.2625 0.5000 0.5000 0.0 0.0 0.2313 0.2313 MgMg 0.0063 0.0063 0.10 0.10 0.030.03 0.05 0.05 실시예26Example 26 0.2625 0.2625 0.5000 0.5000 0.0 0.0 0.2250 0.2250 MgMg 0.0125 0.0125 0.10 0.10 0.030.03 0.05 0.05 실시예27Example 27 0.2625 0.2625 0.5000 0.5000 0.0 0.0 0.2125 0.2125 MgMg 0.0250 0.0250 0.10 0.10 0.030.03 0.05 0.05 실시예28Example 28 0.2625 0.2625 0.5000 0.5000 0.0 0.0 0.1875 0.1875 MgMg 0.0500 0.0500 0.10 0.10 0.030.03 0.05 0.05 실시예29Example 29 0.2625 0.2625 0.5000 0.5000 0.0 0.0 0.1375 0.1375 MgMg 0.1000 0.1000 0.10 0.10 0.030.03 0.05 0.05 실시예30Example 30 0.2625 0.2625 0.5000 0.5000 0.0 0.0 0.2313 0.2313 NiNi 0.0063 0.0063 0.00 0.00 0.030.03 0.05 0.05 실시예31Example 31 0.2625 0.2625 0.5000 0.5000 0.0 0.0 0.2250 0.2250 NiNi 0.0125 0.0125 0.00 0.00 0.030.03 0.05 0.05 실시예32Example 32 0.2625 0.2625 0.5000 0.5000 0.0 0.0 0.2125 0.2125 NiNi 0.0250 0.0250 0.00 0.00 0.030.03 0.05 0.05 실시예33Example 33 0.2625 0.2625 0.5000 0.5000 0.0 0.0 0.1875 0.1875 NiNi 0.0500 0.0500 0.00 0.00 0.030.03 0.05 0.05 실시예34Example 34 0.2625 0.2625 0.5000 0.5000 0.0 0.0 0.1375 0.1375 NiNi 0.1000 0.1000 0.00 0.00 0.030.03 0.05 0.05 실시예35Example 35 0.2625 0.2625 0.5000 0.5000 0.0 0.0 0.2313 0.2313 CoCo 0.0063 0.0063 0.10 0.10 0.030.03 0.05 0.05 실시예36Example 36 0.2625 0.2625 0.5000 0.5000 0.0 0.0 0.2250 0.2250 CoCo 0.0125 0.0125 0.10 0.10 0.030.03 0.05 0.05 실시예37Example 37 0.2625 0.2625 0.5000 0.5000 0.0 0.0 0.2125 0.2125 CoCo 0.0250 0.0250 0.10 0.10 0.030.03 0.05 0.05 실시예38Example 38 0.2625 0.2625 0.5000 0.5000 0.0 0.0 0.1875 0.1875 CoCo 0.0500 0.0500 0.10 0.10 0.030.03 0.05 0.05 실시예39Example 39 0.2625 0.2625 0.5000 0.5000 0.0 0.0 0.1375 0.1375 CoCo 0.1000 0.1000 0.10 0.10 0.030.03 0.05 0.05 실시예40Example 40 0.2625 0.2625 0.5000 0.5000 0.0 0.0 0.2313 0.2313 MnMn 0.0063 0.0063 0.10 0.10 0.000.00 0.05 0.05 실시예41Example 41 0.2625 0.2625 0.5000 0.5000 0.0 0.0 0.2250 0.2250 MnMn 0.0125 0.0125 0.10 0.10 0.000.00 0.05 0.05 실시예42Example 42 0.2625 0.2625 0.5000 0.5000 0.0 0.0 0.2125 0.2125 MnMn 0.0250 0.0250 0.10 0.10 0.000.00 0.05 0.05 실시예43Example 43 0.2625 0.2625 0.5000 0.5000 0.0 0.0 0.1875 0.1875 MnMn 0.0500 0.0500 0.10 0.10 0.000.00 0.05 0.05 실시예44Example 44 0.2625 0.2625 0.5000 0.5000 0.0 0.0 0.1375 0.1375 MnMn 0.1000 0.1000 0.10 0.10 0.000.00 0.05 0.05

이렇게 하여 얻은 소결시편을 양면을 잘 연마한 후, 유전율과 품질계수는 5~7 GHz에서 네트워크 분석기(HP 0571B)를 이용하여 하키-콜만(Hakki-Coleman)의 평행도체판법(Postresonator method)으로 측정하였으며, 공진 주파수 온도계수는 20~80℃의 측정온도 범위에서 공동 공진기법(Cavity method)으로 측정하였다.After polishing both sides of the sintered specimen thus obtained, the dielectric constant and quality factor were measured by the Hockey-Coleman Postresonator method using a network analyzer (HP 0571B) at 5 to 7 GHz. Resonant frequency temperature coefficient was measured by the cavity method (Cavity method) in the measurement temperature range of 20 ~ 80 ℃.

각 시편의 마이크로파 유전특성은 표 3 및 표 4와 같다.
Microwave dielectric characteristics of each specimen are shown in Tables 3 and 4.

소결온도(℃)Sintering temperature (℃) 유전율permittivity 품질계수(GHz)Quality Factor (GHz) 공진주파수 온도계수
(ppm/℃)Resonant frequency
(ppm / DEG C) 비교예1Comparative Example 1 1380 1380 40.0 40.0 35248 35248 -6.5 -6.5 실시예1Example 1 1300 1300 39.6 39.6 47796 47796 -7.8 -7.8 실시예2Example 2 1300 1300 40.5 40.5 48907 48907 -17.5 -17.5 실시예3Example 3 1300 1300 43.2 43.2 46214 46214 -2.2 -2.2 실시예4Example 4 1300 1300 47.2 47.2 34936 34936 33.9 33.9 실시예5Example 5 1300 1300 43.8 43.8 48581 48581 -2.9 -2.9 실시예6Example 6 1300 1300 44.3 44.3 46992 46992 1.3 1.3 실시예7Example 7 1300 1300 44.5 44.5 46009 46009 5.7 5.7 실시예8Example 8 1300 1300 44.8 44.8 45790 45790 8.1 8.1 실시예9Example 9 1300 1300 45.2 45.2 45040 45040 9.9 9.9 실시예10Example 10 1300 1300 45.4 45.4 44754 44754 13.9 13.9 실시예11Example 11 1300 1300 44.8 44.8 45407 45407 6.2 6.2 실시예12Example 12 1300 1300 45.7 45.7 43398 43398 17.6 17.6 실시예13Example 13 1300 1300 45.7 45.7 41847 41847 22.2 22.2 실시예14Example 14 1300 1300 42.7 42.7 27864 27864 33.9 33.9 실시예15Example 15 1300 1300 44.0 44.0 46458 46458 -1.0 -1.0 실시예16Example 16 1300 1300 44.4 44.4 47405 47405 0.8 0.8 실시예17Example 17 1300 1300 44.6 44.6 46918 46918 2.3 2.3 실시예18Example 18 1300 1300 44.5 44.5 45702 45702 3.8 3.8 실시예19Example 19 1300 1300 44.7 44.7 45227 45227 5.2 5.2

실시예Example 소결온도(℃)Sintering temperature (℃) 유전율permittivity 품질계수(GHz)Quality Factor (GHz) 공진주파수 온도계수
(ppm/℃)Resonant frequency
(ppm / DEG C) 비교예2Comparative Example 2 1340 1340 43.8 43.8 36152 36152 -9.2 -9.2 실시예20Example 20 1280 1280 43.7 43.7 48081 48081 -10.6 -10.6 실시예21Example 21 1280 1280 43.4 43.4 47857 47857 -8.5 -8.5 실시예22Example 22 1280 1280 42.4 42.4 46835 46835 -7.9 -7.9 실시예23Example 23 1280 1280 40.6 40.6 45170 45170 -5.3 -5.3 실시예24Example 24 1260 1260 36.5 36.5 16309 16309 13.4 13.4 실시예25Example 25 1300 1300 43.8 43.8 48460 48460 -9.1 -9.1 실시예26Example 26 1300 1300 43.5 43.5 47181 47181 -6.8 -6.8 실시예27Example 27 1300 1300 43.2 43.2 48083 48083 -2.1 -2.1 실시예28Example 28 1280 1280 42.2 42.2 43616 43616 6.1 6.1 실시예29Example 29 1260 1260 37.8 37.8 13528 13528 27.3 27.3 실시예30Example 30 1280 1280 43.8 43.8 48460 48460 -3.3 -3.3 실시예31Example 31 1280 1280 43.5 43.5 47181 47181 5.9 5.9 실시예32Example 32 1280 1280 43.2 43.2 48083 48083 20.9 20.9 실시예33Example 33 1280 1280 42.2 42.2 43616 43616 46.0 46.0 실시예34Example 34 1260 1260 37.8 37.8 13528 13528 78.5 78.5 실시예35Example 35 1280 1280 43.8 43.8 47623 47623 -5.4 -5.4 실시예36Example 36 1280 1280 44.8 44.8 42024 42024 14.6 14.6 실시예37Example 37 1280 1280 44.2 44.2 43774 43774 12.7 12.7 실시예38Example 38 1280 1280 44.5 44.5 38058 38058 31.9 31.9 실시예39Example 39 1260 1260 42.8 42.8 31984 31984 60.6 60.6 실시예40Example 40 1280 1280 44.3 44.3 41475 41475 -1.1 -1.1 실시예41Example 41 1280 1280 43.2 43.2 40432 40432 -6.5 -6.5 실시예42Example 42 1280 1280 42.7 42.7 36808 36808 -5.7 -5.7 실시예43Example 43 1280 1280 39.1 39.1 25059 25059 -0.7 -0.7 실시예44Example 44 1260 1260 37.4 37.4 10386 10386 28.6 28.6

상기 표 3 및 표 4에서 확인되는 바와 같이 본 발명 실시예에 따른 유전체 세라믹은 높은 유전율과 품질계수를 나타내었다. 또한 ANb2O6와 BWO4의 몰비를 변화시킴으로써 안정된 공진 주파수의 온도계수조절이 가능하였다.
As confirmed in Table 3 and Table 4, the dielectric ceramic according to the embodiment of the present invention exhibited high dielectric constant and quality factor. In addition, by changing the molar ratio of ANb 2 O 6 and BWO 4 , it was possible to adjust the temperature coefficient of stable resonance frequency.

Claims (8)

하기의 조성식으로 표시되는 고주파용 유전체 세라믹스 조성물.
ZrO2(a)-TiO2(b)-ANb2O6(c)-BWO4(d)
[0.20≤a≤0.40, 0.50≤b≤0.55, 0.10≤c≤0.30, 0.001≤d≤0.20이고, A=(Zn1-xMgx;0.0≤x≤0.8) B=Zn, Mg, Ni, Mn 또는 Co임] A dielectric ceramic composition for high frequency represented by the following compositional formula.
ZrO 2 (a) -TiO 2 (b) -ANb 2 O 6 (c) -BWO 4 (d)
[0.20 ≦ a ≦ 0.40, 0.50 ≦ b ≦ 0.55, 0.10 ≦ c ≦ 0.30, 0.001 ≦ d ≦ 0.20, and A = (Zn 1-x Mg x ; 0.0 ≦ x ≦ 0.8) B = Zn, Mg, Ni, Mn or Co] 제 1항에 있어서, 상기 조성물에 NiO, MnCO3 및 Y2O3 로 이루어지는 군으로부터 선택되는 적어도 하나를 전체 조성물에 대하여 0.1∼0.3중량% 첨가하는 것을 특징으로 하는 고주파용 유전체 세라믹스 조성물.According to claim 1, wherein the composition is NiO, MnCO 3 And 0.1 to 0.3% by weight based on the total composition of at least one selected from the group consisting of Y 2 O 3 . 제 1항에 있어서, 상기 조성물은 1200 ~ 1300℃의 온도에서 소결되는 것을 특징으로 하는 마이크로파 유전체 세라믹스 조성물.The microwave dielectric ceramic composition according to claim 1, wherein the composition is sintered at a temperature of 1200 to 1300 ° C. ZrO2, TiO2, ANb2O6(A=Zn1 - xMgx;0.0≤x≤0.8), BWO4(B=Zn, Mg, Ni, Mn, Co)를 혼합 후 대기 중에서 900~1100℃의 온도에서 2~4시간 하소하는 단계;
NiO, MnCO3 및 Y2O3로 이루어지는 군으로부터 선택되는 적어도 하나의 첨가제를 첨가하여 습식분쇄 하는 단계;
가압성형하여 성형체를 얻는 단계; 및
상기 성형체를 대기 중에서 1200~1300℃의 온도에서 3~12시간 동안 소결하는 단계를 포함하는 고주파용 유전체의 제조방법.ZrO 2 , TiO 2 , ANb 2 O 6 (A = Zn 1 - x Mg x ; 0.0≤x≤0.8) and BWO 4 (B = Zn, Mg, Ni, Mn, Co) after mixing in the air at the temperature of 900 ~ 1100 ℃ 4 hours calcining;
NiO, MnCO 3 Wet grinding by adding at least one additive selected from the group consisting of Y 2 O 3 ;
Pressing to obtain a molded product; And
A method for producing a dielectric for high frequency comprising the step of sintering the molded body in the air at a temperature of 1200 ~ 1300 ℃ for 3 to 12 hours. 제4항에 있어서, 상기 ZrO2, TiO2, ANb2O6(A=Zn1 - xMgx;0.0≤x≤0.8), BWO4(B=Zn, Mg, Ni, Mn, Co)는 0.20~0.40 : 0.50~0.55 : 0.10~0.30 : 0.001~0.20의 비율로 혼합되는 것을 특징으로 하는 고주파용 유전체의 제조방법.The method of claim 4, wherein the ZrO 2 , TiO 2 , ANb 2 O 6 (A = Zn 1 - x Mg x ; 0.0≤x≤0.8), BWO 4 (B = Zn, Mg, Ni, Mn, Co) is 0.20 to 0.40: 0.50 to 0.55: 0.10 to 0.30: 0.001 A method for producing a high frequency dielectric, characterized in that the mixing at a ratio of ~ 0.20. 제4항에 있어서, 상기 첨가제는 전체 조성물에 대하여 0.1~0.3중량%의 비율로 첨가되는 것을 특징으로 하는 고주파용 유전체의 제조방법.The method of claim 4, wherein the additive is added in a proportion of 0.1 to 0.3% by weight based on the total composition. 제4항에 있어서, 상기 고주파용 유전체는 유전율(Er)>40의 유전특성을 가지는 것임을 특징으로 하는 고주파용 유전체의 제조방법.5. The method of claim 4, wherein the high frequency dielectric has a dielectric property of dielectric constant (Er)> 40. 제4항에 있어서, 상기 고주파용 유전체는 품질계수(Q×F)>45,000의 유전특성을 가지는 것임을 특징으로 하는 고주파용 유전체의 제조방법.

The method of claim 4, wherein the high frequency dielectric has a dielectric constant of quality factor (Q × F)> 45,000.

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* Cited by examiner, † Cited by third party
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