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KR20000050797A - Process for Preparing PFN Dielectric Ceramics with High Dielectric Constant and Low Dielectric Loss - Google Patents

Process for Preparing PFN Dielectric Ceramics with High Dielectric Constant and Low Dielectric Loss Download PDF

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KR20000050797A
KR20000050797A KR1019990000904A KR19990000904A KR20000050797A KR 20000050797 A KR20000050797 A KR 20000050797A KR 1019990000904 A KR1019990000904 A KR 1019990000904A KR 19990000904 A KR19990000904 A KR 19990000904A KR 20000050797 A KR20000050797 A KR 20000050797A
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박재관
김병국
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박호군
한국과학기술연구원
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Abstract

본 발명은 고 유전율이면서도 유전 손실이 극소화된 순수한 Pb(Fe1/2Nb1/2)O3(ＰＦＮ) 유전체 세라믹스의 새로운 제조 방법을 제공하는 것이다. 본 발명의 ＰＦＮ계 유전체 세라믹스의 제조 방법은 통상의 고상 반응법에 따라 ＰＦＮ계 유전체 세라믹스 분말을 제조한 후, 첨가제의 혼입 없이 산소 분위기에서 하소 및 소결시키는 것을 특징으로 한다. 본 발명에 따르면, 하소 및 소결 공정의 제어만으로 고유전율이면서도 유전 손실이 극소화된 순수한 ＰＦＮ 유전체 세라믹스를 얻을 수 있다.The present invention provides a novel method for producing pure Pb (Fe 1/2 Nb 1/2 ) O 3 (PFN) dielectric ceramics with high dielectric constant and minimal dielectric loss. The method for producing a PNP-based dielectric ceramics of the present invention is characterized by producing a PNP-based dielectric ceramic powder according to a conventional solid-phase reaction method, and then calcining and sintering in an oxygen atmosphere without incorporation of additives. According to the present invention, pure PNP dielectric ceramics with high dielectric constant and minimum dielectric loss can be obtained only by controlling the calcination and sintering processes.

Description

고 유전율, 저 유전 손실의 ＰＦＮ 유전체 세라믹스의 제조 방법{Process for Preparing PFN Dielectric Ceramics with High Dielectric Constant and Low Dielectric Loss}Process for Preparing PFN Dielectric Ceramics with High Dielectric Constant and Low Dielectric Loss

본 발명은 고 유전율이면서도 유전 손실이 극소화된 순수한 Pb(Fe1/2Nb1/2)O3(ＰＦＮ) 유전체 세라믹스의 새로운 제조 방법을 제공하는 것이다. 보다 구체적으로, 본 발명은 통상의 고상 반응법에 따라 ＰＦＮ계 유전체 세라믹스 분말을 제조한 후, 유전 손실을 줄이기 위한 첨가제의 혼입 없이 산소 분위기 하에서 하소 및 소결시키는 것을 특징으로 하는 ＰＦＮ계 유전체 세라믹스의 제조 방법에 관한 것이다. 본 발명에 따르면, 통상의 고상 반응법에 따라 첨가제의 혼입 없이 하소 및 소결 공정의 제어만으로 고 유전율이면서도 유전 손실이 극소화된 ＰＦＮ 유전체 세라믹스를 얻을 수 있다.The present invention provides a novel method for producing pure Pb (Fe 1/2 Nb 1/2 ) O 3 (PFN) dielectric ceramics with high dielectric constant and minimal dielectric loss. More specifically, the present invention is to prepare a PNP-based dielectric ceramics powder according to the conventional solid-phase reaction method, and then calcined and sintered in an oxygen atmosphere without incorporation of additives for reducing dielectric loss. It is about a method. According to the present invention, PNP dielectric ceramics having a high dielectric constant and minimizing dielectric loss can be obtained only by controlling the calcination and sintering processes without incorporating additives according to a conventional solid phase reaction method.

적층형 세라믹 콘덴서(Multi-Layer Ceramic Capacitor)는 작고 가벼운 전자회로를 구성하는데 있어서 필수적인 수동 부품이다. 현재까지 적층형 세라믹 콘덴서의 제조에 있어서 BaTiO3를 중심으로 한 티탄산(titanate)계가 주로 사용되어 왔다. 그러나, 이런 재료들은 일반적으로 1300℃ 이상의 높은 소결 온도에서 제조되므로, Pd, Pt 등과 같은 값비싼 귀금속 내부 전극을 필요로 한다. 이러한 값비싼 전극을 사용하는 데 따른 비용을 줄이기 위해서는 Ag, Ag-Pd 등의 값싼 전극을 사용할 수 있는 저온 소결용 유전체 세라믹스 조성물이 필요하게 된다.Multi-Layer Ceramic Capacitors are an essential passive component for building small, lightweight electronic circuits. Until now, titanate based on BaTiO 3 has been mainly used in the manufacture of multilayer ceramic capacitors. However, these materials are generally manufactured at high sintering temperatures of 1300 ° C. or higher, requiring expensive precious metal internal electrodes such as Pd, Pt and the like. In order to reduce the cost of using such an expensive electrode, there is a need for a low-temperature sintered dielectric ceramic composition that can use a cheap electrode such as Ag, Ag-Pd.

Pb계 완화형 강유전체는 티탄산계에 비하여 낮은 온도에서 소결될 수 있으므로, Ag, Ag-Pd 등의 값싼 내부 전극을 사용할 수 있는 조성물이다. 또한, 높은 유전 상수, 완만한 상전이 등의 특징을 갖고 있어서 새로운 적층형 세라믹 콘덴서의 재료로서 각광받고 있다. 그러나, 이러한 Pb계 완화형 강유전체 재료는 Pb의 휘발로 인해 공정 변수에 민감하며 재현성이 떨어진다는 것과 유전 손실이 비교적 크다는 단점이 있다.Since the Pb-based relaxed ferroelectric can be sintered at a lower temperature than the titanic acid-based, a low internal electrode such as Ag or Ag-Pd can be used. In addition, it has high characteristics of dielectric constant, gentle phase transition, and the like, and has attracted much attention as a material for a new multilayer ceramic capacitor. However, these Pb-based relaxed ferroelectric materials have the disadvantages of being sensitive to process variables due to volatilization of Pb, poor reproducibility, and relatively large dielectric losses.

Pb계 복합 페로브스카이트(perovskite) 화합물 중에서 Pb(Fe1/2Nb1/2)O3(ＰＦＮ)계는 1000℃ 이하의 저온에서 소결이 가능하며 유전율이 매우 높을 뿐만 아니라, 완만형 상전이를 나타내므로 유전율의 온도 특성이 우수하다. 또한, 유전율의 주파수 의존성이 없으므로 주파수에 따른 유전 특성의 변화가 작은 것이 특징이다. 그러나, 첨가제가 없는 순수한 ＰＦＮ은 유전 손실이 크다는 단점으로 인하여 적층형 세라믹 콘덴서의 제조에 널리 사용되지 못하고 있다.Among the Pb-based composite perovskite compounds, Pb (Fe 1/2 Nb 1/2 ) O 3 (PFN) system is capable of sintering at low temperature below 1000 ℃, has a very high dielectric constant, and has a slow phase transition. Since the temperature characteristic of dielectric constant is excellent. In addition, since there is no frequency dependence of permittivity, the change in dielectric properties with frequency is small. However, pure PFN without additives has not been widely used in the manufacture of multilayer ceramic capacitors due to the high dielectric loss.

이러한 ＰＦＮ계 유전체 세라믹스의 단점을 극복하기 위하여 종래에는 ＰＦＮ계 유전체 세라믹스를 제조하는 동안 Mn 등과 같은 첨가제를 혼입하여 Fe를 치환함으로써 전도 전자의 농도를 낮추고, 그에 따라 유전 손실을 감소시키는 방법이 제안되었다 (참조: 박경봉, 윤기현, "용융염 합성법에 의한 MnO2가 첨가된 Pb(Fe1/2Nb1/2)O3의 유전성", 한국요업학회지, 28[1] 79-85 (1991)).In order to overcome the drawbacks of the PNP-based dielectric ceramics, a method of lowering the concentration of conduction electrons by incorporating additives such as Mn and the like and replacing Fe during the manufacture of the PNP-based dielectric ceramics has been proposed. (Reference: Kyung Bong Park, Ki-Hyun Yoon, "Dielectricity of Pb (Fe 1/2 Nb 1/2 ) O 3 with MnO 2 by Molten Salt Synthesis Method," Journal of the Korean Ceramic Society, 28 [1] 79-85 (1991)) .

그러나, 지금까지 첨가제가 혼입되지 않은 순수한 ＰＦＮ계 유전체 세라믹스를 제조함에 있어서 유전 손실을 줄이는 방법은 알려져 있지 않다.However, until now, there is no known method of reducing dielectric loss in producing pure PFN-based dielectric ceramics in which additives are not incorporated.

따라서, 본 발명의 목적은 첨가제의 사용없이 고 유전율이면서도 유전 손실이 극소화된 순수한 ＰＦＮ계 유전체 세라믹스를 950℃ 이하의 저온에서 고상 반응법에 의해 합성하는 방법을 제공하는 것을 목적으로 한다.Accordingly, an object of the present invention is to provide a method for synthesizing pure PF-based dielectric ceramics having a high dielectric constant and minimizing dielectric loss without using an additive by a solid phase reaction method at a low temperature of 950 ° C or lower.

상기 본 발명의 목적은,The object of the present invention,

통상의 고상 반응법에 따라 Fe2O3, Nb2O5및 PbO로부터 Pb(Fe1/2Nb1/2)O3(ＰＦＮ)분말을 제공하는 단계,Providing Pb (Fe 1/2 Nb 1/2 ) O 3 (PFN) powder from Fe 2 O 3 , Nb 2 O 5 and PbO according to a conventional solid phase reaction method,

상기 ＰＦＮ 분말을 산소 분위기 하에 하소시키는 단계, 및Calcining the PNP powder under an oxygen atmosphere, and

상기 하소시킨 ＰＦＮ 분말을 성형한 후 산소 분위기 하에 950 ℃ 이하의 온도에서 소결시키는 단계Molding the calcined PNP powder and sintering at a temperature of 950 ° C. or less under an oxygen atmosphere

를 포함하는, 유전 손실을 줄이기 위한 첨가제의 혼입이 없는 순수한 ＰＦＮ계 유전체 세라믹스의 제조 방법에 의해 달성된다.It is achieved by a method for producing a pure PNP-based dielectric ceramics, including no additives to reduce the dielectric loss.

이하, 본 발명에 따른 고 유전율, 저 유전 손실의 순수한 ＰＦＮ계 유전체 세라믹스 제조 방법을 상세히 설명한다.Hereinafter, a high dielectric constant, low dielectric loss pure PNP-based dielectric ceramic manufacturing method according to the present invention will be described in detail.

본 발명의 방법에 따라 순수한 ＰＦＮ계 유전체 세라믹스를 제조하기 위한 출발원료로는 PbO, Fe2O3, Nb2O5를 사용하며, 순도 약 99.9% 이상의 고순도의 것을 사용하는 것이 좋다.PbO, Fe 2 O 3 , Nb 2 O 5 is used as a starting material for producing pure PNP dielectric ceramics according to the method of the present invention, and it is preferable to use a high purity of about 99.9% or more.

고상 반응법에 따라 먼저, Fe2O3와 Nb2O5를 약 1:1의 몰비로 칭량한 후, 에틸알콜과 지르코니아볼을 사용하여 습식 혼합한다. 혼합된 슬러리를 건조한 후 열처리하여 FeNbO4상을 합성한다. 이어서, FeNbO4분말과 PbO를 약 1:2의 몰비로 칭량한 후 FeNbO4상을 합성할 때와 같은 방법으로 습식 혼합한다. 이 후, 건조 과정을 거쳐서 하소시킨다. 하소는 산소 분위기 하에 약 850 ℃에서 수행한다.According to the solid phase reaction, Fe 2 O 3 and Nb 2 O 5 are first weighed in a molar ratio of about 1: 1, and then wet mixed using ethyl alcohol and zirconia ball. The mixed slurry is dried and then heat treated to synthesize a FeNbO 4 phase. Subsequently, the FeNbO 4 powder and the PbO are weighed in a molar ratio of about 1: 2, and then wet mixed in the same manner as in the synthesis of the FeNbO 4 phase. Thereafter, it is calcined through a drying process. Calcination is carried out at about 850 ° C. under an oxygen atmosphere.

이와 같이 준비된 ＰＦＮ 분말에 바인더로서 폴리비닐알콜(PVA) 수용액을 첨가하여 조립화한 다음, 성형한다. 성형은 가압 성형에 이은 정수압 성형에 의해 수행된다. 얻어진 성형체에서 PVA 바인더를 제거한 후 소결시킨다. 소결은 성형체를 산소 분위기 하에, 상온으로부터 약 300℃/hr로 소결 온도까지 승온시키고 2 시간 동안 유지한 후 로냉시킴으로써 수행된다. 소결 온도는 약 900℃ ∼ 950℃, 바람직하기로는 약 925℃이다.A polyvinyl alcohol (PVA) aqueous solution is added to the PNP powder thus prepared as a binder, granulated, and molded. Molding is carried out by pressure molding followed by hydrostatic molding. The obtained molded body is removed and then sintered. Sintering is carried out by heating the molded body under an oxygen atmosphere at room temperature from about 300 ° C./hr up to the sintering temperature and holding for 2 hours, followed by quenching. The sintering temperature is about 900 ° C to 950 ° C, preferably about 925 ° C.

이하, 실시예에 의해 본 발명을 더욱 구체적으로 설명한다.Hereinafter, the present invention will be described in more detail with reference to Examples.

〈실시예〉<Example>

먼저, 순도 약 99.9%의 Fe2O3와 Nb2O5를 약 1:1의 몰비로 청량한 후, 에틸알콜과 지르코니아볼을 사용하여 약 24시간 동안 습식 혼합하였다. 혼합된 슬러리를 건조한 후 약 1000℃에서 약 4시간 동안 열처리하여 FeNbO4상을 합성하였다. 이어서, 얻어진 FeNbO4분말과 순도 약 99.9%의 PbO를 약 1:2의 몰비로 칭량하여 FeNbO4상을 합성할 때와 같은 방법으로 약 24 시간 동안 습식 혼합하였다. 이 후, 건조 과정을 거쳐서 약 850 ℃에서 약 2시간 동안 하소시켰다. 이 때의 하소 분위기는 공기 또는 산소 (O2) 1기압으로 하였다.First, Fe 2 O 3 and Nb 2 O 5 having a purity of about 99.9% were refreshed at a molar ratio of about 1: 1, and then wet mixed for about 24 hours using ethyl alcohol and zirconia ball. The mixed slurry was dried and then heat treated at about 1000 ° C. for about 4 hours to synthesize a FeNbO 4 phase. Subsequently, the obtained FeNbO 4 powder and PbO having a purity of about 99.9% were weighed in a molar ratio of about 1: 2 and wet mixed for about 24 hours in the same manner as in the synthesis of the FeNbO 4 phase. Thereafter, it was calcined at about 850 ° C. for about 2 hours through a drying process. The calcination atmosphere at this time was made into air or oxygen (O 2 ) 1 atm.

이같이 준비된 ＰＦＮ 분말의 성형을 돕기 위해 농도가 약 5 wt%인 PVA 수용액을 약 2 wt% 첨가한 후, 100 메시 표준체를 이용하여 조립화하였다. 조립화된 ＰＦＮ 분말을 지름 15 mm의 몰드를 이용하여 30 MPa의 압력으로 일축 가압 성형한 후, 다시 200 MPa의 압력으로 정수압 성형하였다. 얻어진 성형체를 약 500℃에서 약 2시간 유지하여 PVA 바인더를 제거한 후, 상온으로부터 약 300℃/hr로 소결 온도까지 승온시키고 2 시간 동안 유지한 후 로냉시켰다. 이 때의 소결 분위기 역시 공기 또는 산소(O2) 1기압으로 하였다.In order to assist the molding of the thus prepared PNP powder, about 2 wt% of an aqueous PVA solution having a concentration of about 5 wt% was added, and then granulated using a 100 mesh standard. The granulated PNP powder was uniaxially press-molded at a pressure of 30 MPa using a mold having a diameter of 15 mm, and then hydrostatically molded at a pressure of 200 MPa. The obtained molded body was held at about 500 ° C. for about 2 hours to remove the PVA binder, and then heated to about 300 ° C./hr from normal temperature to sintering temperature, held for 2 hours, and then cooled by furnace. Sintering atmosphere at this time was also the air or oxygen (O 2) 1 atm.

소결한 후 최종적인 시편의 두께가 1 mm가 되도록 SiC 연마지 (#1000, #2000)를 이용하여 연마하였다. 연마 후, 은 페이스트를 시편의 양쪽 면에 바르고 약 600 ℃에서 약 30분간 열처리하여 전극을 형성하였다.After sintering, polishing was performed using SiC abrasive paper (# 1000, # 2000) so that the final specimen thickness was 1 mm. After polishing, silver paste was applied to both sides of the specimen and heat treated at about 600 ° C. for about 30 minutes to form electrodes.

얻어진 시편의 유전 특성은 저주파 임피던스 분석기(LF impedance analyzer; Hewlett Packard 사 제품, 모델명 HP 4129A)를 사용하여 1.0 Vrms, 1 KHz에서 측정하였다. 그 결과를 하기 표 1에 나타내었다.Dielectric properties of the obtained specimens were measured at 1.0 V rms , 1 KHz using a low frequency impedance analyzer (HP 4129A, model name Hewlett Packard). The results are shown in Table 1 below.

ＰＦＮ 유전체 세라믹스의 소결 온도와 하소 및 소결 분위기에 따르는 유전 특성Dielectric Properties According to Sintering Temperature and Calcining and Sintering Atmosphere of PPF Dielectric Ceramics NoNo 소결온도 (℃)Sintering Temperature (℃) 하소 분위기Calcination atmosphere 소결 분위기Sintering atmosphere 유전상수Dielectric constant 유전손실(%)Dielectric loss (%) 1One 900900 공기air 공기air 1600016000 0.500.50 22 900900 공기air 산소Oxygen 1800018000 0.200.20 33 900900 산소Oxygen 공기air 1700017000 0.400.40 44 900900 산소Oxygen 산소Oxygen 1900019000 0.150.15 55 925925 공기air 공기air 2000020000 0.200.20 66 925925 공기air 산소Oxygen 2500025000 0.0050.005 77 925925 산소Oxygen 공기air 2100021000 0.150.15 88 925925 산소Oxygen 산소Oxygen 2700027000 0.0050.005 99 950950 공기air 공기air 1900019000 0.300.30 1010 950950 공기air 산소Oxygen 2000020000 0.020.02 1111 950950 산소Oxygen 공기air 1900019000 0.200.20 1212 950950 산소Oxygen 산소Oxygen 2200022000 0.020.02 *하소온도: 850℃* Calcining temperature: 850 ℃

상기 표 1의 결과에서 소결 온도가 같을 경우에 하소-공기 분위기, 소결-공기 분위기; 하소-산소 분위기, 소결-공기 분위기; 하소-공기 분위기, 소결-산소 분위기; 하소-산소 분위기, 소결-산소 분위기의 순으로 고 유전율, 저 유전 손실의 ＰＦＮ 유전체 세라믹스를 얻을 수 있었다. 또, 하소-산소 분위기, 소결-산소 분위기일 경우, 약 925℃의 소결 온도에서 가장 큰 유전율과 가장 작은 유전 손실의 ＰＦＮ 유전체 세라믹스를 얻을 수 있었다. 이와 같은 ＰＦＮ의 고 유전율, 저 유전 손실화는 산소 분위기 하에서의 하소 및 소결로 인하여 Fe3+에서 Fe2+로의 환원이 억제되는데에 기인하는 것으로 보인다. 즉, 산소 분위기 소결에 의하여 Fe3+에서 Fe2+로의 환원이 억제됨으로써 전도 전자와 전하 보상을 위한 격자 결함의 농도가 공기 분위기 소결의 그 것들에 비하여 감소하게 됨으로써 양호한 유전 특성을 갖게 되는 것으로 판단된다.Calcination-air atmosphere, sintering-air atmosphere when the sintering temperature is the same as the result of Table 1; Calcination-oxygen atmosphere, sintering-air atmosphere; Calcination-air atmosphere, sintering-oxygen atmosphere; High dielectric constant, low dielectric loss PNP dielectric ceramics were obtained in the order of calcination-oxygen atmosphere and sintering-oxygen atmosphere. In the case of a calcination-oxygen atmosphere and a sintering-oxygen atmosphere, PFR dielectric ceramics having the largest dielectric constant and the smallest dielectric loss were obtained at a sintering temperature of about 925 ° C. This high dielectric constant and low dielectric loss of the PNP seems to be due to the suppression of the reduction of Fe 3+ to Fe 2+ due to calcination and sintering in an oxygen atmosphere. That is, the reduction of Fe 3+ to Fe 2+ by oxygen atmosphere sintering is suppressed, so that the concentration of lattice defects for conduction electrons and charge compensation is reduced compared to those of air atmosphere sintering, and thus it is judged to have good dielectric properties. do.

본 발명에 따르면, 종래의 고상 반응법에 따른 ＰＦＮ의 제조 과정에서 높은 유전 손실을 억제하기 위해 Mn 등과 같은 첨가제를 혼입시킬 필요 없이 하소 및 소결 공정의 제어만으로 고 유전율이면서도 유전 손실이 극소화된 ＰＦＮ 소결체를 얻을 수 있다.According to the present invention, in order to suppress the high dielectric loss in the manufacturing process of the conventional solid state reaction method, the Pn sintered body has a high dielectric constant and minimizes dielectric loss only by controlling the calcination and sintering process without the need to add an additive such as Mn. Can be obtained.

Claims (2)

Fe2O3, Nb2O5및 PbO로부터 Pb(Fe1/2Nb1/2)O3(ＰＦＮ) 분말을 제공하는 단계,Providing a Pb (Fe 1/2 Nb 1/2 ) O 3 (PFN) powder from Fe 2 O 3 , Nb 2 O 5 and PbO, 상기 ＰＦＮ 분말을 산소 분위기 하에 하소시키는 단계, 및Calcining the PNP powder under an oxygen atmosphere, and 상기 하소시킨 ＰＦＮ 분말을 성형한 후 산소 분위기 하에 950 ℃ 이하의 온도에서 소결시키는 단계Molding the calcined PNP powder and sintering at a temperature of 950 ° C. or less under an oxygen atmosphere 를 포함하는, 유전 손실을 줄이기 위한 첨가제의 혼입이 없는 순수한 ＰＦＮ 유전체 세라믹스의 제조 방법.A method of producing a pure PNP dielectric ceramics, including a mixture of additives to reduce dielectric loss. 상기 제1항에 있어서, 소결 온도가 900∼950℃인 ＰＦＮ 유전체 세라믹스의 제조 방법.The method for producing a PNP dielectric ceramic according to claim 1, wherein the sintering temperature is 900 to 950 ° C.
KR1019990000904A 1999-01-15 1999-01-15 Process for Preparing PFN Dielectric Ceramics with High Dielectric Constant and Low Dielectric Loss Expired - Fee Related KR100310275B1 (en)

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