KR100462873B1 - Piezoelectric ceramic composition and piezoelectric device using the same - Google Patents

Piezoelectric ceramic composition and piezoelectric device using the same Download PDF

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KR100462873B1
KR100462873B1 KR10-2001-0086417A KR20010086417A KR100462873B1 KR 100462873 B1 KR100462873 B1 KR 100462873B1 KR 20010086417 A KR20010086417 A KR 20010086417A KR 100462873 B1 KR100462873 B1 KR 100462873B1
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권상구
허강헌
홍종국
서동환
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주식회사 에스세라
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Abstract

본 발명은 일반식이 [Pb(1-1.5x)±(0∼0.2)Lax][Ti(1-y-z)MnyCuz]O3으로 표현되고, 상기 일반식의 하첨자는 각각 0.03≤x≤0.13, 0.0001≤y≤0.1, 및 0.0001≤z≤0.1을 만족하는 주성분에, 첨가제로서 CoO, MgO, ZnO, Al2O3, Fe2O3, Cr2O3,Sb2O3, SnO2, CeO2, Nb2O5, V2O5및 WO3로 구성된 그룹 중 적어도 하나의 성분을 0.01wt%이상 2wt%이하를 첨가한 압전 세라믹 조성물을 제공한다.In the present invention, the general formula is represented by [Pb (1-1.5x) ± (0∼0.2) La x ] [Ti (1-yz) Mn y Cu z ] O 3 , and the subscripts of the general formula are 0.03 ≦ x, respectively. CoO, MgO, ZnO, Al 2 O 3 , Fe 2 O 3 , Cr 2 O 3 , Sb 2 O 3 , SnO as main additives satisfying ≤0.13, 0.0001≤y≤0.1, and 0.0001≤z≤0.1 Provided is a piezoelectric ceramic composition in which at least one component of the group consisting of 2 , CeO 2 , Nb 2 O 5 , V 2 O 5, and WO 3 is added in an amount of 0.01 wt% or more and 2 wt% or less.

본 발명의 압전체 세라믹 조성물은 산소분압 80% 이상의 분위기가 아닌 대기압에서도 안정적인 소결이 가능하며, 우수한 압전특성뿐만 아니라 열적 안정성을 갖는다. 따라서, 전극형성면적을 작은 세라믹 공진기에서도 15㎒이상의 고주파화가 가능한 두께 종진동 3 고조파의 우수한 압전특성을 갖는 조성물을 얻을 수 있다.The piezoelectric ceramic composition of the present invention is capable of stable sintering at atmospheric pressure in an atmosphere having an oxygen partial pressure of 80% or more, and has excellent piezoelectric properties as well as thermal stability. Therefore, a composition having excellent piezoelectric characteristics of thickness longitudinal vibration 3 harmonics capable of high frequency of 15 MHz or more even in a ceramic resonator having a small electrode formation area can be obtained.

Description

압전 세라믹 조성물과 그 압전 세라믹 조성물을 이용한 압전소자{PIEZOELECTRIC CERAMIC COMPOSITION AND PIEZOELECTRIC DEVICE USING THE SAME}Piezoelectric ceramic composition and piezoelectric element using the piezoelectric ceramic composition {PIEZOELECTRIC CERAMIC COMPOSITION AND PIEZOELECTRIC DEVICE USING THE SAME}

본 발명은 압전 세라믹 조성물에 관한 것으로서, 특히 종래의 압전 세라믹 성분을 다른 성분으로 치환시키고 양이온의 전자가수가 2 내지 6인 첨가제를 선택하여 첨가시킴으로써 높은 D/R(dynamic ratio)값을 나타내는 우수한 압전특성을 갖는 압전 세라믹 조성물과 이를 이용한 압전 세라믹 소자에 관한 것이다.BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a piezoelectric ceramic composition, and in particular, an excellent piezoelectric material exhibiting high D / R (dynamic ratio) values by replacing a conventional piezoelectric ceramic component with another component and selecting and adding an additive having an electron valence of 2 to 6 It relates to a piezoelectric ceramic composition having a characteristic and a piezoelectric ceramic device using the same.

최근 정보 산업의 발달에 따라, 하드디스크 드라이브(HDD). HHP. 시디롬(CD-ROM). 씨디 판독기록장치(CD-RW). 디비디(DVD), 디비디 판독기록장치(DVD-RW), 무선 키보드, 광마우스 등 거의 모든 가전기기 및 설비에는 클럭 주파수를 발생시키는 표면실장(SMD)형 공진기가 디지탈 시대의 핵심 부품의 하나로 사용된다. 이러한 공진기는 디지털 제품의 성능향상과 소형에 따라 고주파화, 경박단소화를 추구하면서 계속적으로 발전하고 있다. 따라서, 보다 고주파화되고 소형화된 공진기를 제조하기 위해 보다 우수한 압전특성과 온도안정성을 갖는 압전 세라믹 조성물이 요구된다.With the recent development of the information industry, hard disk drives (HDD). HHP. CD-ROM. CD-RW. Nearly all home appliances and equipment, such as DVDs, DVD-RWs, wireless keyboards, optical mice, etc., use surface mount resonators that generate clock frequencies as one of the key components of the digital era. . These resonators continue to develop while pursuing high frequency and light and small size reduction in accordance with the performance and small size of digital products. Therefore, there is a need for a piezoelectric ceramic composition having better piezoelectric properties and temperature stability to fabricate a higher frequency and miniaturized resonator.

최근에 많이 활용되는 압전 세라믹 조성물은 Pb(Zr,Ti)O3계와 PbTiO3계의 두 종류로 대별할 수 있다. 이러한 압전 세라믹 조성물의 대표적인 진동모드는 두께 진동모드이다. 이는 진동시 에너지 트랩을 이용하는 것으로, 기본파의 진동을 사용하는 방식과 고차진동을 사용하는 방식이 있다.Piezoelectric ceramic compositions which are widely used in recent years can be roughly classified into two types, Pb (Zr, Ti) O 3 and PbTiO 3 . A typical vibration mode of such piezoelectric ceramic composition is a thickness vibration mode. It uses energy traps during vibration, and there is a method using vibration of fundamental wave and a method using higher order vibration.

Pb(Zr,Ti)O3계의 경우, 기본파의 진동에서는 아주 우수하나 고차진동에서는 상대적으로 압전특성이 떨어지며 공진주파수 상수가 상대적으로 작으므로, 높은 주파수를 얻기 어렵다는 한계가 있다. 이와 달리, PbTiO3계는 유전율이 낮고 입자의 크기가 작으며, 높은 상전이온도를 갖는 특성이 있다. 또한, C축 방향으로 격자 이방성이 크므로, 기본파의 진동에서는 에너지를 트랩하기 어려우나 높은 주파수를 얻을 수 있는 고차진동의 경우는 에너지 트랩이 용이하다. 이러한 특성에 의해, PbTiO3계는 Pb(Zr,Ti)O3계보다 우수한 압전특성 및 온도 안정성을 가지므로, 고주파대역 발진자에 적합한 소재로 인지되고 있다.In the case of Pb (Zr, Ti) O 3 system, it is very good in vibration of fundamental wave, but in high order vibration, piezoelectric characteristics are relatively inferior and the resonant frequency constant is relatively small. Therefore, it is difficult to obtain high frequency. In contrast, the PbTiO 3 system has a low dielectric constant, small particle size, and high phase transition temperature. In addition, since the lattice anisotropy is large in the C-axis direction, it is difficult to trap energy in the vibration of the fundamental wave, but energy trapping is easy in the case of higher-order vibrations in which high frequencies can be obtained. Due to these characteristics, the PbTiO 3 system has better piezoelectric properties and temperature stability than the Pb (Zr, Ti) O 3 system, and thus is known as a suitable material for high frequency band oscillators.

하지만, PbTiO3계는 결정학적인 이방성이 크기 때문에, 냉각시 상전이에 의해 발생하는 자발응력에 의해 쉽게 균열이 발생하여 소결이 불량하다는 문제가 있어, 다양한 성분을 치환하거나 다른 첨가제를 사용하여 냉각시 상전이에 의하여 발생하는 자발응력을 최소화하고, 소결성을 증진시키는 연구가 활발히 진행되고 있다.However, since PbTiO 3 system has a large crystallographic anisotropy, cracking easily occurs due to spontaneous stress generated by phase transition during cooling, resulting in poor sintering, and thus phase transition upon cooling by substituting various components or using other additives. Minimizing the spontaneous stress caused by the, and the research to improve the sintering is being actively conducted.

이러한 대표적인 예로서, 일본 특개평7-206517호(1995.8.8일자 공개, 출원인: 마쯔시타전기주식회사)에는 (Pb,La)TiO3계 주성분에 첨가제로서 CuO, ZrO2, MnO2을 사용한 압전 세라믹 조성물을 제시하고 있다. 상기 문헌에 따르면, 상기 새로운 압전 세라믹 조성물은 높은 사용주파수와 공진시 큰 D/R(dynamic ratio)을 갖는 효과가 있다. 하지만, 그 압전 세라믹 조성물은 산소 분압 80% 이상의 분위기에서 소결시켜야 하며, 그 특성 평가시에 직격 15~18㎜인 소자를 사용하는데, 이는 직경 최근 하드디스크 구동용 세라믹 발진자에서 사용되는 2.5㎜ ×2.0㎜의 40㎒를 초과한 세라믹 레조네이터에 적용하는데 한계가 있다. 또한, 이를 소형화시킬 경우에는 공진시의 D/R이 저하되고 3차 고조파에서 스퓨리어스(spurious)현상이 발생되는 문제가 있다.As a representative example of this, Japanese Patent Laid-Open No. 7-206517 (published on August 8,199, Applicant: Matsushita Electric Co., Ltd.) has a piezoelectric ceramic composition using CuO, ZrO 2 , and MnO 2 as an additive to a (Pb, La) TiO 3 -based main component. Presenting. According to this document, the new piezoelectric ceramic composition has an effect of having a high dynamic ratio (D / R) at high operating frequencies and resonance. However, the piezoelectric ceramic composition should be sintered in an atmosphere with an oxygen partial pressure of 80% or more, and when evaluating its properties, an element having a straight line of 15 to 18 mm is used, which is 2.5 mm × 2.0 in diameter recently used in ceramic oscillators for driving hard disks. There is a limit to application to ceramic resonators exceeding 40 MHz of mm. In addition, when miniaturization thereof, there is a problem in that the D / R at resonance decreases and spurious phenomenon occurs in the third harmonic.

본 발명은 상기 문제점을 해결하기 위해서 안출된 것으로, 본 발명의 일 목적은 압전소자에 적용할 때에 전극형성면적을 2.5㎜ ×2.0㎜ 이하로 작게 하여도, 대기압 상에서도 소결이 가능하면, 약 250℃ 이상의 리플로에서 우수한 전기적 특성(D/R 60이상) 및 열적 특성을 갖고, 두께 종진동 3차 고조파의 우수한 압전 특성을 나타내는 압전 세라믹 조성물을 제공하는데 있다.SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and one object of the present invention is to reduce the electrode formation area to 2.5 mm x 2.0 mm or less when applied to piezoelectric elements. To provide a piezoelectric ceramic composition having excellent electrical properties (D / R 60 or more) and thermal properties in the above reflow, and excellent piezoelectric properties of the third longitudinal harmonics of thickness vibration.

또한, 본 발명의 다른 목적은 고주파화와 소형화에 유리하면서 고온에서 표면실장이 가능한 압전 세라믹 소자를 제공하는데 있다.In addition, another object of the present invention is to provide a piezoelectric ceramic device which is surface mountable at high temperature while being advantageous for high frequency and miniaturization.

본 발명은, 일반식이 [Pb(1-1.5x)±(0∼0.2)Lax][Ti(1-y-z)MnyCuz]O3으로 표현되고, 상기 일반식의 하첨자는 각각 0.03≤x≤0.13, 0.0001≤y≤0.1, 및 0.0001≤z≤0.1을 만족하는 주성분에, 첨가제로서 CoO, MgO, ZnO, Al2O3, Fe2O3, Cr2O3,Sb2O3, SnO2, CeO2, Nb2O5, V2O5및 WO3로 구성된 그룹 중 적어도 하나의 성분을 0.01wt%이상 2wt%이하를 첨가한 압전세라믹 조성물을 제공한다.In the present invention, a general formula is represented by [Pb (1-1.5x) ± (0 to 0.2) La x ] [Ti (1-yz) Mn y Cu z ] O 3 , and the subscripts of the general formula are 0.03 ≦. In the main components satisfying x≤0.13, 0.0001≤y≤0.1, and 0.0001≤z≤0.1, CoO, MgO, ZnO, Al 2 O 3 , Fe 2 O 3 , Cr 2 O 3 , Sb 2 O 3 , Provided is a piezoceramic composition in which at least one component of the group consisting of SnO 2 , CeO 2 , Nb 2 O 5 , V 2 O 5, and WO 3 is added in an amount of 0.01 wt% or more and 2 wt% or less.

또한, 본 발명은 상기 압전 세라믹 조성물을 이용하여 고주파화와 소형화에 유리하면서 고온에서도 표면실장이 가능한 압전 세라믹 소자를 제공한다.In addition, the present invention provides a piezoelectric ceramic device that can be surface-mounted at a high temperature while being advantageous for high frequency and miniaturization using the piezoelectric ceramic composition.

본 발명의 압전체 조성범위는, ABO3복합페로브스카이트(perovskite)의 조성에서 A사이트의 성분을 PbO, La2O3로 구성하고, B사이트의 성분을 TiO2, MnO2및, CuO로 구성한 일반식 [Pb(1-1.5x)±(0∼0.2)Lax][Ti(1-y-z)MnyCuz]O3을 주성분으로 하고, 첨가제로서 CoO, MgO, ZnO, Al2O3, Fe2O3, Cr2O3,Sb2O3, SnO2, CeO2, Nb2O5, V2O5및 WO3로 구성된 그룹 중 적어도 하나의 성분이 0.01wt%이상 2wt%이하 첨가된다.In the piezoelectric composition range of the present invention, the component of A site is composed of PbO and La 2 O 3 in the composition of ABO 3 composite perovskite, and the component of B site is composed of TiO 2 , MnO 2, and CuO. Constituent general formula [Pb (1-1.5x) ± (0∼0.2) La x ] [Ti (1-yz) Mn y Cu z ] O 3 as a main component, and CoO, MgO, ZnO, Al 2 O as an additive 3 , Fe 2 O 3 , Cr 2 O 3 , Sb 2 O 3 , SnO 2 , CeO 2 , Nb 2 O 5 , V 2 O 5 And WO 3 At least one component of the group consisting of 0.01wt% or more 2wt% It is added below.

이와 같이, 종래의 압전 세라믹 조성물과 달리 망간(Mn)과 구리(Cu)를 첨가제로서 투입하는 것이 아니라, 매트릭스 조성으로 티타늄(Ti) 성분 대신에 치환하여 결정구조 및 화학적 안정성과 함께 입내와 입계의 전하중성을 보다 안정적으로 조절시킨다. 또한, 첨가제로서 CoO, MgO, ZnO, Al2O3, Fe2O3, Cr2O3,Sb2O3, SnO2, CeO2, Nb2O5, V2O5및 WO3로 구성된 그룹 중 적어도 하나의 성분을 0.01wt%이상 2wt%이하를 투입함으로써 압전특성을 보다 향상시킬 수 있다.As described above, unlike conventional piezoelectric ceramic compositions, manganese (Mn) and copper (Cu) are not added as additives, but instead of titanium (Ti) in a matrix composition, the crystal structure and chemical stability of the grain and grain boundary Adjust charge neutrality more stably. In addition, it is composed of CoO, MgO, ZnO, Al 2 O 3 , Fe 2 O 3 , Cr 2 O 3 , Sb 2 O 3 , SnO 2 , CeO 2 , Nb 2 O 5 , V 2 O 5 and WO 3 The piezoelectric properties may be further improved by adding 0.01 wt% or more and 2 wt% or less to at least one component of the group.

상기 일반식에서, A사이트의 구성 원소인 란탄(La)은 하첨자 x가 0.03 내지 0.13 범위가 되도록 포함된다. 란탄(La)을 0.03이상 투입하면, 납(Pb)이 차지하던 일부 자리에 공동을 형성하여 전하중성을 유지한다. 이로써, 원자의 확산이 촉진되어 소결시에 결정학적 이방성으로 인한 내부응력을 완화시키고 균열을 방지할 수 있다. 하지만, 란탄 함유량이 0.03미만이면 그러한 효과가 떨어지며, 0.13을 초과하면, 발진안정성과 열적 안정성이 저하되는 경향이 있다.In the general formula, lanthanum (La), which is a constituent element of the A site, is included so that the subscript x is in the range of 0.03 to 0.13. When lanthanum (La) is added to 0.03 or more, a cavity is formed at some sites occupied by lead (Pb) to maintain charge neutrality. As a result, the diffusion of atoms may be promoted to alleviate internal stress due to crystallographic anisotropy during sintering and to prevent cracking. However, when the lanthanum content is less than 0.03, such an effect is inferior, and when it exceeds 0.13, there exists a tendency for oscillation stability and thermal stability to fall.

또한, 상기 일반식에서 B사이트의 구성요소인 망간(Mn)과 구리(Cu)는 미세한 변화에 의해 압전 세라믹 조성물의 전기적인 특성과 열적 안정성을 향상시키는 역할을 한다. 망간은 하첨자 y가 0.0001 내지 0.1 범위가 되도록 포함된다. 상기 범위를 초과하면, 전자의 어셉터로 작용하여 소결체의 절연성이 저하되고 누설전류의 양이 급격히 증가하여 분극이 불가능하거나 압전특성이 저하되는 문제가 있다. 또한, 구리는 하첨자 z가 0.0001 내지 0.1 범위가 되도록 포함된다. 상기 범위에서 상기 조성물에 필수적인 성분으로 공동을 제공하여 공진저항값을 낮추어 누설전류를 제어한다. 상기 범위를 초과하면, 압전특성이 저하되며, 열적 안정성이 저하되는 문제가 있다.Further, in the general formula, manganese (Mn) and copper (Cu), which are components of the B-site, serve to improve electrical characteristics and thermal stability of the piezoelectric ceramic composition by minute changes. Manganese is included such that the subscript y is in the range 0.0001 to 0.1. If it exceeds the above range, there is a problem that the insulating property of the sintered compact and acts as an electron acceptor and the amount of leakage current is rapidly increased, so that polarization is impossible or the piezoelectric properties are degraded. Copper is also included so that the subscript z is in the range of 0.0001 to 0.1. In the above range, the cavity is provided as an essential component of the composition to control the leakage current by lowering the resonance resistance value. If it exceeds the above range, there is a problem that the piezoelectric properties are lowered and the thermal stability is lowered.

첨가제인 경우에는, CoO, MgO, ZnO, Al2O3, Fe2O3, Cr2O3,Sb2O3, SnO2, CeO2, Nb2O5, V2O5및 WO3로 구성된 그룹 중 선택된 어느 성분을 첨가하더라도, 압전특성이 향상하다가, 감소하는 경향이 나타났다. 상기 선택된 조성에 따라 그 차이는 있었으나, 약 0.01wt%이상 2wt%이하범위에서는 압전특성이 향상되는 경향을 나타내었다. 특히, 첨가제가 2wt%를 초과하면, 소결체의 절연성이 저하되어 분극이 불가능하거나 압전특성이 급격히 떨어지는 문제가 있다.In the case of an additive, CoO, MgO, ZnO, Al 2 O 3 , Fe 2 O 3 , Cr 2 O 3 , Sb 2 O 3 , SnO 2 , CeO 2 , Nb 2 O 5 , V 2 O 5 and WO 3 Addition of any component selected from the group constituted showed a tendency for the piezoelectric properties to improve and then decrease. Although there was a difference according to the selected composition, the piezoelectric properties tended to be improved in the range of about 0.01 wt% or more and 2 wt% or less. In particular, when the additive is more than 2wt%, the insulation of the sintered compact is lowered, so that polarization is impossible or the piezoelectric characteristics are sharply degraded.

본 발명의 압전 세라믹 조성물은, 소결성이 우수하므로 소정의 산소분압을 갖는 분위기에서 소결하지 않고 대기압 하에서도 안정적인 소결이 가능할 뿐만 아니라, 표면실장을 위한 250℃ 이상의 리플로에서도 우수한 전기적 특성을 가지며, 리플로 후에도 열적 안정성이 우수하다. 따라서, 고주파화가 가능한 두께 종진동 3고조파의 우수한 압전특성을 나타낼 뿐만 아니라, 평면치수가 2.5㎜ ×2.0㎜이하인 전극형성면을 갖는 압전 세라믹 소자로 제조가능한 조성물로 제공될 수 있다.Since the piezoelectric ceramic composition of the present invention is excellent in sintering property, it is possible not only to sinter in an atmosphere having a predetermined oxygen partial pressure but to be stable sintering under atmospheric pressure, and to have excellent electrical properties even in a reflow of 250 ° C. or higher for surface mounting. The thermal stability is excellent even after furnace. Therefore, it is possible to provide a composition that can be manufactured from a piezoelectric ceramic device having an electrode-forming surface having a planar dimension of 2.5 mm x 2.0 mm or less, as well as exhibiting excellent piezoelectric properties of the thickness longitudinal vibration 3 harmonics capable of high frequency.

이하, 하기 표들을 참조하여, 실험예들을 통해 본 발명을 보다 상세히 설명한다.<실험예들>Hereinafter, the present invention will be described in more detail with reference to the following tables.

출발원료 PbO, La2O3, TiO2, MnO2, CuO와, 첨가제로서 CoO, MgO, ZnO, Al2O3, Fe2O3, Cr2O3,Sb2O3, SnO2, CeO2, Nb2O5, V2O5및 WO3로 구성된 그룹 중 적어도 하나의성분을 각각 평량하였다 표에 나타낸 조성이 되도록 볼밀을 이용하여 혼합하였다. 충분히 혼합된 슬러리를 그 파우더의 입경이 0.1 - 1.5㎛가 되도록 유지하면서 건조시킨다. 건조시에는 층분리가 발생되지 않도록 주의해야 한다. 층분리가 발생되면, 페로브스카이트 결정이 단일상으로 형성되지 않고, 2상으로 형성되어 압전특성에 치명적인 영향을 주며, 파우더의 평균입경이 상기 범위를 벗어나면, 단일상 형성을 위한 적합한 에너지를 공급할 수 없으므로, 제2 상이 형성되거나 미반응상 원료 파우더가 발생된다.Starting materials PbO, La 2 O 3 , TiO 2 , MnO 2 , CuO and as additives CoO, MgO, ZnO, Al 2 O 3 , Fe 2 O 3 , Cr 2 O 3 , Sb 2 O 3 , SnO 2 , CeO At least one component of the group consisting of 2 , Nb 2 O 5 , V 2 O 5, and WO 3 was weighed, respectively. Mixing was carried out using a ball mill to obtain the composition shown in the table. The sufficiently mixed slurry is dried while maintaining the particle size of the powder to 0.1-1.5 탆. Care should be taken when drying to avoid delamination. When delamination occurs, the perovskite crystals are not formed in a single phase, but are formed in two phases and have a fatal effect on the piezoelectric properties, and when the average particle diameter of the powder is out of the above range, suitable energy for forming a single phase is obtained. Since the second phase is not formed, unreacted raw material powder is generated.

이어, 상기 파우더를 650-1000℃ 전후에서 1-4시간 동안 하소하였다. 단일 상의 형성되지 않도록 2단계 하소법을 선택하였다. 얻어진 하소분을 소량의 바인더를 혼합하여 평균입경이 0.1 - 1.2㎛의 크기로 습식분쇄한 후에 대기상태 분위기에서 1000 - 1350℃의 소성온도로 1시간 내지 4시간동안 소성하여 23㎜ ×18㎜의 판상 소결체를 얻었다. 얻어진 소결체를 1차적으로 0.5㎜두께로 양면연마한 후에, 2차적으로 두께 종진동 3차모드가 20㎒ - 60㎒ 범위를 갖도록 표면조도가 우수한 압전체로 가공하였다. 다음으로, 얻어진 압전체를 양면에 직경 0.5-1.5㎜인 전극을 형성하여 압전체 시료를 제조하였다. 이 시료는 100-250℃의 실리콘 오일 속에서 3-10㎸㎜의 전계를 10-30분간 인가하여 분극 처리를 하였다.The powder was then calcined at 650-1000 ° C. for 1-4 hours. The two step calcination method was chosen such that no single phase was formed. The obtained calcined powder was mixed with a small amount of binder and wet pulverized to an average particle size of 0.1-1.2 탆, and then calcined at 1000-1350 DEG C for 1 to 4 hours in an atmospheric condition to be 23 mm x 18 mm A plate-shaped sintered compact was obtained. After the obtained sintered body was first polished on both sides with a thickness of 0.5 mm, it was secondarily processed into a piezoelectric material having excellent surface roughness so that the thickness longitudinal vibration third mode had a range of 20 MHz to 60 MHz. Next, the piezoelectric sample was prepared by forming electrodes having a diameter of 0.5-1.5 mm on both surfaces of the obtained piezoelectric body. This sample was subjected to polarization treatment by applying an electric field of 3-10 μm for 10-30 minutes in 100-250 ° C. silicone oil.

이와 같이 마련된 각각의 시편을 임피던스분석기(제품명: HP4194A)를 사용하여 에너지 트랩을 이용한 두께 종진동 3고조파의 공진주파수 부근에서 공진주파수(Fr), 반공진주파수(Fa), 공진저항(Zr), 반공진저항(Za)를 측정하였다.Each specimen prepared as described above was subjected to an impedance analyzer (product name: HP4194A) using the energy trap, and the resonance frequency (F r ), the anti-resonance frequency (F a ), and the resonance resistance (Z) near the resonance frequency of the three longitudinal harmonics of the thickness longitudinal vibration. r ) and antiresonance resistance (Z a ) were measured.

본 실험에서는 유전율, 전자기계결합계수(kt) 및, 기계적 품질계수(Qm)보다는 실제 발진기에서 발진회로구현시 출력레벨을 결정하는 D/R(dynamic ratio)과 발진안정성의 중요한 인자인 공진주파수의 온도계수(TCF) 및 상전이온도와 그 온도에서 표면실장 리플로우 후에 발진주파수의 변화율(△Fosc)을 중심으로 평가하였다.In this experiment, resonance, which is an important factor of D / R (dynamic ratio) and oscillation stability, is used to determine the output level of oscillation circuit in the actual oscillator rather than the dielectric constant, electromechanical coupling coefficient (k t ) and mechanical quality coefficient (Q m ). The temperature coefficient (TCF) and phase transition temperature of the frequency and the rate of change of the oscillation frequency ( ΔF osc ) after the surface mount reflow at the temperature were evaluated.

D/R값은 아래 식과 같이 표현되는 출력레벨을 결정하는 인자로서, 본 실험에서는 두께 종 진동 3차 고조포 모드로 I.R.E의 표준회로로 측정하였다.The D / R value is a factor that determines the output level expressed as the following equation. In this experiment, it was measured by the standard circuit of I.R.E.

공진주파수 온도계수(TCF)는 -40℃ ∼ 90℃ 범위에서 공진주파수(Fr)를 측정하여 아래 식으로 를 계산하였다.The resonance frequency temperature coefficient (TCF) was measured by the following equation by measuring the resonance frequency (F r ) in the range of -40 ℃ ~ 90 ℃.

전술한 결과로 얻어진 압전특성 및 온도특성들을 각각 다른 조성비로 이루어진 압전체 시편과 함께 정리하여 표1과 표2로 나타내었다.The piezoelectric and temperature characteristics obtained as described above are summarized together with the piezoelectric specimens having different composition ratios, respectively, and are shown in Tables 1 and 2.

표1은 동일한 조성범위를 갖는 주성분에서 첨가제의 종류와 양을 달리하여 제조한 시편의 평가 결과이다.Table 1 shows the evaluation results of specimens prepared by varying the type and amount of additives in the main components having the same composition range.

시료번호Sample Number [Pb(1-1.5x)±(0∼0.2)Lax][Ti(1-y-z)MnyCuz]O3 [Pb (1-1.5x) ± (0∼0.2) La x ] [Ti (1-yz) Mn y Cu z ] O 3 첨가제additive 첨가량(wt%)Addition amount (wt%) D/R(dB)D / R (dB) TCF(ppm/℃)TCF (ppm / ° C) Tc(℃)T c (℃) △Fosc(%) ΔF osc (%) 비고Remarks xx yy zz 1*One* 0.020.02 0.020.02 0.00550.0055 없음none 5555 1313 390390 0.0050.005 2*2* 0.020.02 0.020.02 0.00550.0055 CoOCoO 0.010.01 5151 88 385385 0.0050.005 3*3 * 0.020.02 0.020.02 0.00550.0055 CoOCoO 0.020.02 4848 1212 384384 0.0070.007 4*4* 0.020.02 0.020.02 0.00550.0055 CoOCoO 0.050.05 4141 1414 384384 0.010.01 5*5 * 0.020.02 0.020.02 0.00550.0055 CoOCoO 2.02.0 4343 1313 384384 0.010.01 6*6 * 0.020.02 0.020.02 0.00550.0055 CoOCoO 2.52.5 분극불가Non-polarization 7*7 * 0.020.02 0.020.02 0.00550.0055 MgOMgO 0.010.01 5252 1212 381381 0.060.06 88 0.030.03 0.020.02 0.00550.0055 MgOMgO 22 6060 77 360360 0.060.06 99 0.030.03 0.020.02 0.00550.0055 ZnOZnO 0.010.01 6262 1111 385385 0.010.01 1010 0.030.03 0.020.02 0.00550.0055 ZnOZnO 22 6464 1212 382382 0.020.02 1111 0.030.03 0.020.02 0.00550.0055 Al2O3 Al 2 O 3 0.010.01 6363 1414 382382 0.010.01 12*12 * 0.030.03 0.020.02 0.00550.0055 Al2O3 Al 2 O 3 22 5858 1313 385385 0.010.01 1313 0.030.03 0.020.02 0.00550.0055 Fe2O3 Fe 2 O 3 0.050.05 6565 1010 380380 0.0050.005 1414 0.030.03 0.020.02 0.00550.0055 Fe2O3 Fe 2 O 3 22 6565 1515 382382 0.0070.007 1515 0.030.03 0.020.02 0.00550.0055 Cr2O3 Cr 2 O 3 0.010.01 6363 77 385385 0.010.01 1616 0.030.03 0.020.02 0.00550.0055 Cr2O3 Cr 2 O 3 22 6262 1313 384384 0.0050.005 1717 0.030.03 0.020.02 0.00550.0055 Sb2O3 Sb 2 O 3 0.050.05 6565 1212 385385 0.0050.005 1818 0.030.03 0.020.02 0.00550.0055 Sb2O3 Sb 2 O 3 22 6464 88 381381 0.0070.007 1919 0.030.03 0.020.02 0.00550.0055 SnO2 SnO 2 0.050.05 6565 66 380380 0.0090.009 2020 0.030.03 0.020.02 0.00550.0055 SnO2 SnO 2 22 6868 77 378378 0.010.01 2121 0.030.03 0.020.02 0.00550.0055 CeO2 CeO 2 0.050.05 6565 55 380380 0.0070.007 2222 0.030.03 0.020.02 0.00550.0055 CeO2 CeO 2 22 6262 88 379379 0.010.01 2323 0.030.03 0.020.02 0.00550.0055 Nb2O5 Nb 2 O 5 0.010.01 6262 1010 385385 0.010.01 2424 0.030.03 0.020.02 0.00550.0055 Nb2O5 Nb 2 O 5 22 6262 1212 378378 0.0070.007 2525 0.030.03 0.020.02 0.00550.0055 V2O5 V 2 O 5 0.010.01 6161 1414 388388 0.0090.009 2626 0.030.03 0.020.02 0.00550.0055 V2O5 V 2 O 5 22 4545 66 385385 0.010.01 2727 0.030.03 0.020.02 0.0050.005 WO3 WO 3 0.050.05 6565 88 385385 0.030.03 2828 0.030.03 0.020.02 0.0050.005 WO3 WO 3 22 6666 1515 381381 0.010.01

(비교예는 *로 표시됨)(Comparative example is marked with *)

상기 표1에 나타난 바와 같이, 압전특성을 나타내는 D/R값에서, 첨가제를 투입하지 않은 비교예인 시편 1보다 첨가제를 투입한 경우에 60dB에서 65dB로 증가하였다. 첨가제의 종류에 따라 그 정도는 달리하였으나, 대체로 첨가제로서 CoO, Fe2O3, Sb2O3, SnO2, CeO2및 WO3을 첨가할 때에 그 개선폭이 크다는 것을 알 수 있었다. 상기 첨가제는 일부가 이온반경과 허용인자(tolerance factor)에 따라 주성분의 매트릭스에 치환되고 일부는 입계에 존재할 수도 있다. 이로 인해, 표1과 같이, 결정학적 이방성과 압전특성에 영향을 받아 D/R 특성은 일정범위에서 증가하지만, 공진주파수 온도계수는 약간 감소하는 경향을 나타낸다. 하지만, 첨가제에 의해 감소되는 공진주파수 온도계수 30ppm/℃범위내의 값을 가지므로 원하는 발진안정성에는 큰 영향을 미치지 않는 것으로 나타났다.As shown in Table 1, in the D / R value showing the piezoelectric properties, the additive was increased from 60dB to 65dB when the additive is added to the specimen 1, the comparative example without the additive. Although the degree was different depending on the type of the additive, it was found that the improvement was large when adding CoO, Fe 2 O 3 , Sb 2 O 3 , SnO 2 , CeO 2 and WO 3 as additives. The additive may be partially substituted in the matrix of the main component and some may be present at the grain boundaries depending on the ionic radius and tolerance factor. For this reason, as shown in Table 1, the D / R characteristic increases in a certain range under the influence of crystallographic anisotropy and piezoelectric characteristics, but the resonance frequency temperature coefficient tends to decrease slightly. However, since it has a value within the 30ppm / ℃ range of the resonance frequency temperature coefficient is reduced by the additive did not appear to have a significant effect on the desired oscillation stability.

이러한 첨가제는 주성분을 기준으로 0.01 내지 2wt%범위를 첨가하는 것이 바람직하다. 첨가제의 양이 0.01wt%에서는 그 효과가 미비하였으며, 2wt%를 초과하면, 소결체의 절연성이 저하되어 분극이 불가능하거나 압전특성이 급격히 저하되었다.Such additives are preferably added in the range of 0.01 to 2wt% based on the main component. If the amount of the additive is 0.01wt%, the effect is insignificant, and if it exceeds 2wt%, the insulation of the sintered body is lowered and polarization is impossible or the piezoelectric characteristic is sharply lowered.

표2는 CoO, MgO, ZnO, Al2O3, Fe2O3, Cr2O3,Sb2O3, SnO2, CeO2, Nb2O5, V2O5및 WO3로 구성된 그룹 중 하나의 첨가제를 0.01wt%이상 2wt%이하의 양으로 첨가하되, 주성분의 조성범위를 달리하여 제조된 시편의 평가결과이다.Table 2 shows the group consisting of CoO, MgO, ZnO, Al 2 O 3 , Fe 2 O 3 , Cr 2 O 3 , Sb 2 O 3 , SnO 2 , CeO 2 , Nb 2 O 5 , V 2 O 5 and WO 3 One of the additives is added in an amount of 0.01wt% or more and less than 2wt%, but the evaluation result of the specimen prepared by varying the composition range of the main component.

시료번호Sample Number [Pb(1-1.5x)±(0∼0.2)Lax][Ti(1-y-z)MnyCuz]O3 [Pb (1-1.5x) ± (0∼0.2) La x ] [Ti (1-yz) Mn y Cu z ] O 3 첨가제additive 첨가량(wt%)Addition amount (wt%) D/R(dB)D / R (dB) TCF(ppm/℃)TCF (ppm / ° C) Tc(℃)T c (℃) △Fosc(%) ΔF osc (%) 비고Remarks xx yy zz 1*One* 00 00 0.010.01 CoOCoO 0.0010.001 소결불가Cannot be sintered 2*2* 00 00 0.10.1 CoOCoO 0.010.01 소결불가Cannot be sintered 3*3 * 00 0.10.1 00 CoOCoO 0.10.1 소결불가Cannot be sintered 4*4* 0.020.02 0.020.02 0.00010.0001 CoOCoO 0.050.05 5151 88 385385 0.0050.005 5*5 * 0.020.02 0.10.1 0.00850.0085 CoOCoO 2.02.0 3838 1111 388388 0.0070.007 6*6 * 0.020.02 0.00010.0001 0.0050.005 MgOMgO 0.010.01 5959 1010 385385 0.0080.008 7*7 * 0.020.02 0.020.02 0.00550.0055 ZnOZnO 0.010.01 4545 1111 385385 0.010.01 88 0.070.07 0.010.01 0.00250.0025 Al2O3 Al 2 O 3 0.010.01 6868 77 345345 0.010.01 99 0.070.07 0.040.04 0.00850.0085 Fe2O3 Fe 2 O 3 22 7171 1313 347347 0.010.01 1010 0.070.07 0.020.02 0.00550.0055 Cr2O3 Cr 2 O 3 0.010.01 5050 77 340340 0.010.01 11*11 * 0.070.07 0.040.04 0.00850.0085 Sb2O3 Sb 2 O 3 22 4848 1313 324324 0.020.02 12*12 * 0.070.07 0.010.01 0.0040.004 SnO2 SnO 2 0.010.01 3535 77 315315 0.0090.009 13*13 * 0.070.07 0.020.02 0.00550.0055 CeO2 CeO 2 0.050.05 4141 1515 339339 0.0070.007 1414 0.070.07 0.030.03 0.00650.0065 CeO2 CeO 2 1One 6868 44 337337 0.0080.008 1515 0.070.07 0.040.04 0.010.01 CeO2 CeO 2 22 6666 1212 336336 0.0090.009 1616 0.120.12 0.020.02 0.00550.0055 Nb2O5 Nb 2 O 5 0.010.01 6868 1111 292292 0.030.03 1717 0.120.12 0.020.02 0.00550.0055 V2O5 V 2 O 5 22 6868 1010 290290 0.020.02 18*18 * 0.120.12 0.040.04 0.00850.0085 WO3 WO 3 22 3737 66 290290 0.010.01 1919 0.120.12 0.010.01 0.00250.0025 Al2O3 Al 2 O 3 0.010.01 6969 1111 290290 0.010.01 2020 0.120.12 0.020.02 0.00550.0055 Al2O3 Al 2 O 3 22 6363 1717 291291 0.010.01 2121 0.120.12 0.010.01 0.00350.0035 Fe2O3 Fe 2 O 3 0.010.01 6262 1313 292292 0.010.01 22*22 * 0.160.16 0.020.02 0.00550.0055 Fe2O3 Fe 2 O 3 0.050.05 6363 4545 245245 0.0050.005 23*23 * 0.160.16 0.030.03 0.00650.0065 Fe2O3 Fe 2 O 3 1One 5454 5252 251251 0.010.01 24*24 * 0.160.16 0.040.04 0.0080.008 Fe2O3 Fe 2 O 3 22 3030 4444 247247 0.0090.009 25*25 * 0.160.16 0.020.02 0.00550.0055 Cr2O3 Cr 2 O 3 0.010.01 5555 3737 248248 0.120.12 26*26 * 0.160.16 0.030.03 0.00850.0085 Cr2O3 Cr 2 O 3 22 4040 4949 244244 0.040.04 27*27 * 0.200.20 0.010.01 0.00350.0035 Sb2O3 Sb 2 O 3 0.010.01 3232 5252 245245 0.080.08 28*28 * 0.200.20 0.020.02 0.00550.0055 Sb2O3 Sb 2 O 3 0.50.5 2828 6262 246246 0.090.09 29*29 * 0.200.20 0.030.03 0.00650.0065 Sb2O3 Sb 2 O 3 1One 3939 6868 245245 0.070.07 30*30 * 0.200.20 0.040.04 0.0080.008 Sb2O3 Sb 2 O 3 22 3838 6969 240240 0.090.09 31*31 * 0.200.20 0.010.01 0.00450.0045 SnO2 SnO 2 0.010.01 4141 6262 245245 0.10.1 32*32 * 0.200.20 0.020.02 0.00550.0055 SnO2 SnO 2 0.50.5 3737 7272 246246 0.110.11 33*33 * 0.220.22 00 00 SnO2 SnO 2 0.10.1 분극불가Non-polarization 34*34 * 00 0.120.12 00 CoOCoO 0.30.3 분극불가Non-polarization 35*35 * 00 00 0.120.12 Sb2O3 Sb 2 O 3 0.50.5 분극불가Non-polarization

(비교예는 *로 표시됨)(Comparative example is marked with *)

상기 표2에 나타낸 바와 같이, 납성분을 치환한 란탄의 몰수인 x가 0.03 내지 0.13범위에 있고, 티탄성분을 치환한 망간과 구리의 몰수인 y와 z가 0.0001 내지 0.1범위에 있을 때에, 대기압 하에서도 안정적인 소결이 가능하며, 15㎒이상의 고주파가 가능한 두께 종진동 3고조파의 우수한 압전특성 및 온도 안정성을 나타내었다.As shown in Table 2, when the molar number x of the lanthanum substituted with the lead component is in the range of 0.03 to 0.13, and the molar number y and z of the manganese and copper substituted with the titanium component is in the range of 0.0001 to 0.1, atmospheric pressure Stable sintering is possible under the condition, and the excellent piezoelectric properties and temperature stability of the thickness longitudinal vibration 3 harmonics with high frequency of 15MHz or more are shown.

란탄은 3 내지 13㏖%의 범위에서 내부응력을 완화시켜 균열을 방지하는 역할을 한다. 란탄함유량이 3㏖%이상일 때에 소결성이 향상되고, D/R값은 증가하는 경향을 나타냈으나, 13㏖%를 초과할 때에 공진주파수 온도계수(TCF)는 60ppm/℃이상 초과하면서 상전이온도도 감소하는 경향을 나타낸다.Lanthanum serves to prevent cracking by relaxing internal stress in the range of 3 to 13 mol%. When the lanthanum content was 3 mol% or more, the sinterability improved and the D / R value tended to increase. However, when the lanthanum content was more than 13 mol%, the resonance frequency temperature coefficient (TCF) exceeded 60 ppm / ° C and the phase transition temperature was also increased. It tends to decrease.

망간은 0.01 내지 10㏖%의 범위에서 공진저항을 낮추어 압전특성을 개선하고 내열성을 향상시켜 열적 안정성을 부여한다. 망간함유량이 0.01㏖%미만일 때는 그 효과가 미비하며, 10㏖%를 초과할 때는 절연성이 저항되어 누설전류양이 급격히 증가하여 분극이 불가능하게 된다.Manganese lowers the resonance resistance in the range of 0.01 to 10 mol%, thereby improving piezoelectric properties and improving heat resistance to impart thermal stability. If the manganese content is less than 0.01 mol%, the effect is insignificant. If it exceeds 10 mol%, the insulation resistance is increased and the amount of leakage current rapidly increases, making polarization impossible.

또한, 상기 조성물의 필수적인 구성 중 하나인 구리는 4가의 원소로서 결정구조에서 공동을 제공함으로써 공진저항을 낮추어 누설전류를 제어하는 역할을 하며, 그 함유량이 증가할수록 공진주파수 온도계수도 다소 감소하는 경향을 나타내었다. 구리함유량이 0.01㏖%미만에서는 효과가 미비하며, 10㏖%를 초과하면, 압전특성이 저하된다.In addition, copper, which is one of the essential components of the composition, serves to control the leakage current by lowering the resonance resistance by providing a cavity in the crystal structure as a tetravalent element, and as the content thereof increases, the resonance frequency temperature coefficient also tends to decrease somewhat. Indicated. If the copper content is less than 0.01 mol%, the effect is insignificant, and if it exceeds 10 mol%, the piezoelectric properties are lowered.

한편, 표1에 나타난 바와 같이, CoO, MgO, ZnO, Al2O3, Fe2O3, Cr2O3,Sb2O3,SnO2, CeO2, Nb2O5, V2O5및 WO3중에서 선택된 첨가제는 0.01 내지 2wt%범위를 첨가하는 것이 바람직하다. 첨가제의 양이 0.01wt%에서는 그 효과가 미비하였으며,2wt%를 초과하면, 소결체의 절연성이 저하되어 분극이 불가능하거나 압전특성이 급격히 저하되었다.Meanwhile, as shown in Table 1, CoO, MgO, ZnO, Al 2 O 3 , Fe 2 O 3 , Cr 2 O 3 , Sb 2 O 3 , SnO 2 , CeO 2 , Nb 2 O 5 , V 2 O 5 And the additive selected from WO 3 is preferably added in the range of 0.01 to 2wt%. If the amount of the additive is 0.01wt%, the effect is insignificant. If it exceeds 2wt%, the insulating property of the sintered body is lowered, so that polarization is impossible or the piezoelectric property is sharply lowered.

이와 같이, 전극형성면의 평면치수 2.5㎜ ×2.0㎜에 적합하게 소형화시켜도, D/R 값은 60dB이상으로 유지되고, 각 조성의 상전이온도(Tc)와 리플로후의 발진주파수변화량(△Fosc)이 ±1 %정도이며, 공진주파수 온도계수(TCF)가 60ppm/℃이하인 특성을 나타낸다.In this way, even if the size of the electrode formation surface is reduced to a size of 2.5 mm x 2.0 mm, the D / R value is maintained at 60 dB or more, and the phase transition temperature T c of each composition and the oscillation frequency change amount after reflow (ΔF) osc ) is ± 1%, and the resonant frequency temperature coefficient (TCF) is 60ppm / ℃ or less.

이상에서 설명한 본 발명은 상술한 실시형태 및 첨부된 도면에 의해 한정되는 것이 아니고, 첨부된 청구범위에 의해 한정된다. 따라서, 청구범위에 기재된 본 발명의 기술적 사상을 벗어나지 않는 범위 내에서 다양한 형태의 치환, 변형 및 변경이 가능하다는 것은 당 기술분야의 통상의 지식을 가진 자에게는 명백할 것이다.The present invention described above is not limited by the above-described embodiment and the accompanying drawings, but by the appended claims. Therefore, it will be apparent to those skilled in the art that various forms of substitution, modification, and alteration are possible without departing from the technical spirit of the present invention described in the claims.

상술한 바와 같이, 본 발명에 따른 압전체 세라믹 조성물은 산소분압 80% 이상의 분위기가 아닌 대기상에서도 안정적인 소결이 가능하며, 250℃이상의 리플로에서도 60dB이상의 높은 전기적 특성을 나타낼 뿐만 아니라, 우수한 열적 안정성을 갖는다. 즉, 리플로 후의 발진주파수 변화량이 1% 내외로 나타내며, 공진주파수 온도계수도 30ppm/℃이하까지 나타나는 우수한 압전 세라믹 조성물을 얻을 수 있다.As described above, the piezoelectric ceramic composition according to the present invention is capable of stable sintering in the atmospheric phase, not in an atmosphere of oxygen partial pressure of 80% or more, exhibits high electrical properties of 60 dB or more even in a reflow of 250 ° C. or more, and has excellent thermal stability. . In other words, it is possible to obtain an excellent piezoelectric ceramic composition exhibiting an oscillation frequency change amount of about 1% after reflow and having a resonance frequency temperature coefficient of 30 ppm / ° C or less.

따라서, 전극형성면적을 작은 세라믹 공진기에서도 15㎒이상의 고주파화가 가능한 두께 종진동 3 고조파의 우수한 압전특성을 갖는 조성물을 얻을 수 있다.Therefore, a composition having excellent piezoelectric characteristics of thickness longitudinal vibration 3 harmonics capable of high frequency of 15 MHz or more even in a ceramic resonator having a small electrode formation area can be obtained.

Claims (2)

일반식이 [Pb(1-1.5x)±(0∼0.2)Lax][Ti(1-y-z)MnyCuz]O3으로 표현되고, 상기 일반식의 하첨자는 각각 0.03≤x≤0.13, 0.0001≤y≤0.1, 및 0.0001≤z≤0.1을 만족하는 주성분에, 첨가제로서 CoO, MgO, ZnO, Al2O3, Fe2O3, Cr2O3,Sb2O3, SnO2, CeO2, Nb2O5, V2O5및 WO3로 구성된 그룹 중 적어도 하나의 성분을 0.01wt%이상 2wt%이하를 첨가한 압전세라믹 조성물.The general formula is represented by [Pb (1-1.5x) ± (0∼0.2) La x ] [Ti (1-yz) Mn y Cu z ] O 3 , and the subscripts of the general formula are 0.03 ≦ x ≦ 0.13, respectively. CoO, MgO, ZnO, Al 2 O 3 , Fe 2 O 3 , Cr 2 O 3 , Sb 2 O 3 , SnO 2 , CeO as additives to the main components satisfying 0.0001 ≦ y ≦ 0.1 and 0.0001 ≦ z ≦ 0.1 2 , Nb 2 O 5 , Piezoceramic composition wherein at least one component of the group consisting of V 2 O 5 and WO 3 added 0.01wt% or more and 2wt% or less. 제1항에 기재된 압전 세라믹 조성물을 사용하여 제조된 것을 특징으로 하는 압전 세라믹 소자.The piezoelectric ceramic element manufactured using the piezoelectric ceramic composition of Claim 1.
KR10-2001-0086417A 2001-12-27 2001-12-27 Piezoelectric ceramic composition and piezoelectric device using the same KR100462873B1 (en)

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