WO2012035935A1 - 誘電体セラミック、積層セラミックコンデンサ、及びこれらの製造方法 - Google Patents

誘電体セラミック、積層セラミックコンデンサ、及びこれらの製造方法 Download PDF

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WO2012035935A1
WO2012035935A1 PCT/JP2011/068942 JP2011068942W WO2012035935A1 WO 2012035935 A1 WO2012035935 A1 WO 2012035935A1 JP 2011068942 W JP2011068942 W JP 2011068942W WO 2012035935 A1 WO2012035935 A1 WO 2012035935A1
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dielectric
ceramic
multilayer ceramic
ceramic capacitor
dielectric ceramic
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PCT/JP2011/068942
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English (en)
French (fr)
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恵 福田
剛之 矢尾
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株式会社村田製作所
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Priority to KR1020137004622A priority Critical patent/KR20130042578A/ko
Priority to JP2012533926A priority patent/JP5733313B2/ja
Priority to CN2011800420021A priority patent/CN103080044A/zh
Publication of WO2012035935A1 publication Critical patent/WO2012035935A1/ja
Priority to US13/753,845 priority patent/US9061944B2/en

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    • Y10T29/435—Solid dielectric type

Definitions

  • the present invention relates to a dielectric ceramic and a manufacturing method thereof.
  • the present invention also relates to a multilayer ceramic capacitor configured using this dielectric ceramic and a method for manufacturing the same.
  • the dielectric layers of multilayer ceramic capacitors are being made thinner.
  • the electric field strength applied per layer becomes relatively high. Therefore, the dielectric ceramic used for the dielectric layer is required to be improved in reliability at the time of voltage application, particularly in the life characteristics of the high temperature load test.
  • Patent Document 1 has a perovskite-type crystal structure containing barium titanate as a main component and rare earth elements, magnesium and manganese as subcomponents, and a composition formula (Ba 1-y RE y ) (Ti 1- ab Mg ao Mn b ) O 3 (RE: rare earth element), each range being 0.06 ⁇ y ⁇ 0.09, 0.03 ⁇ ao ⁇ 0.045, 0.012 ⁇ b ⁇ 0.
  • a dielectric ceramic characterized in that it is represented by 018 is described.
  • Patent Document 1 does not describe the case where the dielectric layer is thinned. Therefore, it is unclear whether the dielectric ceramic disclosed in Patent Document 1 has high reliability when a voltage is applied when the thickness of the dielectric layer is reduced to about 1 ⁇ m.
  • the present invention has been made in view of such a problem.
  • the dielectric layer is further thinned and has a good dielectric property even when a high electric field strength voltage is applied, and has a life characteristic of a high temperature load test.
  • An object of the present invention is to provide an excellent multilayer ceramic capacitor.
  • the dielectric ceramic according to the present invention has a general formula (Ba 1 -xy Ca x Re y ) (Ti 1 -z M z ) O 3 (where Re is La, Ce, Pr, Nd, Sm, Eu, Gd, At least one element selected from Tb, Dy, Ho, Er, Tm, Yb, Lu, and Y, and M is at least one element selected from Mg, Mn, Al, Cr, and Zn) And an average particle diameter of crystal grains containing a compound in the range of 0 ⁇ x ⁇ 0.2, 0.002 ⁇ y ⁇ 0.1, and 0.001 ⁇ z ⁇ 0.05. Is 20 nm or more and 150 nm or less.
  • the dielectric ceramic according to the present invention preferably has an average particle size of 20 nm or more and less than 100 nm.
  • the present invention is formed on the outer surface of the laminate, the laminate having a plurality of dielectric layers that are laminated, and a plurality of internal electrodes formed along the interface between the dielectric layers,
  • the dielectric layer is also directed to a multilayer ceramic capacitor characterized by comprising the above-mentioned dielectric ceramic.
  • a method for producing a dielectric ceramic comprising: molding a powder to obtain a molded body; and firing the molded body to obtain a dielectric ceramic having an average particle diameter of 20 nm to 150 nm. Is also directed.
  • the average particle size is 20 nm or more and less than 100 nm.
  • the present invention is also directed to a method for manufacturing a multilayer ceramic capacitor, comprising the above-described method for manufacturing a dielectric ceramic.
  • the dielectric layer is further thinned and has a high electric field strength by defining the grain size of the crystal particles as described above while having the above composition. Even when a voltage is applied, it is possible to provide a multilayer ceramic capacitor having good dielectric characteristics and excellent life characteristics in a high-temperature load test.
  • FIG. 1 is a cross-sectional view of a multilayer ceramic capacitor according to the present invention.
  • FIG. 1 is a cross-sectional view of a multilayer ceramic capacitor according to the present invention.
  • the multilayer ceramic capacitor 1 includes a multilayer body 5.
  • the stacked body 5 includes a plurality of stacked dielectric layers 2 and a plurality of internal electrodes 3 and 4 formed along interfaces between the plurality of dielectric layers 2. Examples of the material of the internal electrodes 3 and 4 include those containing Ni as a main component.
  • External electrodes 6 and 7 are formed at different positions on the outer surface of the laminate 5. Examples of the material of the external electrodes 6 and 7 include those containing Ag or Cu as a main component. In the multilayer ceramic capacitor shown in FIG. 1, the external electrodes 6 and 7 are formed on the end surfaces of the multilayer body 5 facing each other. The internal electrodes 3 and 4 are electrically connected to the external electrodes 6 and 7, respectively. The internal electrodes 3 and 4 are alternately stacked inside the stacked body 5 via the dielectric layers 2.
  • the multilayer ceramic capacitor 1 may be of a two-terminal type including two external electrodes 6 and 7 or may be of another terminal type including a large number of external electrodes.
  • the dielectric layer 2 has the general formula (Ba 1-xy Ca x Re y ) (Ti 1-z M z ) O 3 (where Re is La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy) And at least one element selected from Ho, Er, Tm, Yb, Lu and Y, and M is at least one element selected from Mg, Mn, Al, Cr and Zn) And a dielectric ceramic containing as a main component a compound in the range of 0 ⁇ x ⁇ 0.2, 0.002 ⁇ y ⁇ 0.1, and 0.001 ⁇ z ⁇ 0.05.
  • the average grain size of the dielectric ceramic crystal particles is set to 20 nm or more and 150 nm or less.
  • the average particle size is 20 nm or more and less than 100 nm, it is possible to provide a multilayer ceramic capacitor having further excellent life characteristics in a high temperature load test.
  • the molar ratio of (Ba, Ca, Re) and (Ti, M) is appropriately set, and is preferably selected in the range of 0.98 to 1.05.
  • Ceramic powder is produced by, for example, a solid phase synthesis method. Specifically, first, compound powders such as oxides, carbonates, chlorides, and metal organic compounds each containing Ba, Ca, Re, Ti, and M, which are constituent elements of the main component, are mixed at a predetermined ratio, Calcinate. In addition to the solid phase synthesis method, a hydrothermal synthesis method, a hydrolysis method, or the like may be applied.
  • the multilayer ceramic capacitor is manufactured as follows, for example.
  • a ceramic slurry is produced using the ceramic powder obtained as described above.
  • a ceramic green sheet is formed by a sheet forming method or the like.
  • a plurality of ceramic green sheets are laminated and then subjected to pressure bonding to obtain a molded body.
  • a molded object is baked.
  • the ceramic powder is fired to obtain a dielectric layer composed of a dielectric ceramic.
  • external electrodes are formed on the end face of the laminate by baking or the like.
  • MgCO 3 , MnCO 3 , Al 2 O 3 , Cr 2 O 3 , and ZnO powders were prepared. These powders were weighed so as to have the composition shown in Table 1 of (Ba 1-xy Ca x Re y ) (Ti 1-z M z ) O 3 , and then mixed for 80 hours by a ball mill. Thereafter, the mixed powder was calcined and synthesized by heat treatment at 1000 ° C.
  • the average particle size of the obtained ceramic powder was about 10 nm. Moreover, according to XRD, the unreacted substance in the ceramic powder was below the detection level. That is, it was confirmed that this ceramic powder was a highly synthesized powder despite being very fine particles.
  • a ceramic green sheet to be a dielectric layer was formed. Specifically, a polyvinyl butyral binder and ethanol were added to the ceramic powder described above, and wet mixed for 24 hours by a ball mill. Thereafter, filtering with a filter was performed to prepare a slurry from which powder having a particle size other than a particle size within a predetermined range was excluded. And this slurry was shape
  • a molded body was produced. Specifically, a conductive paste containing Ni as a main component was screen-printed on a specific ceramic green sheet to form a conductive paste film to be an internal electrode. Then, a plurality of ceramic green sheets on which the conductive paste film was formed were stacked so that the sides from which the conductive paste film was drawn were alternated, and then pressed to obtain a molded body.
  • the compact was fired. Specifically, first, the binder was burned by heating to a temperature of 300 ° C. in a reducing atmosphere. Thereafter, firing was performed at a temperature of 1200 ° C. for 1 hour in a reducing atmosphere composed of H 2 —N 2 —H 2 O gas having an oxygen partial pressure of 10 ⁇ 10 MPa.
  • an external electrode was formed. Specifically, a Cu paste containing B 2 O 3 —Li 2 O—SiO 2 —BaO glass frit was applied to both end faces of the laminate. Then, it heated at the temperature of 800 degreeC in nitrogen atmosphere, and baked Cu paste. In this way, an external electrode electrically connected to the internal electrode was formed.
  • a multilayer ceramic capacitor was produced as described above.
  • the outer dimensions of the multilayer ceramic capacitor are 1.0 mm in length, 0.5 mm in width, and 0.5 mm in thickness.
  • the number of effective dielectric layers is 100, and the number of internal electrodes per dielectric layer is one.
  • the facing area was 0.3 mm 2 .
  • the thickness of the dielectric layer interposed between the internal electrodes was as shown in “Dielectric layer thickness” in Table 2.
  • the average particle size was calculated as follows. First, the multilayer ceramic capacitor according to each sample was fractured, subjected to thermal etching at a temperature of 1000 ° C., and the fractured surface was observed using a scanning microscope. Then, image analysis was performed on the observed image, and the particle diameter of the crystal particles was measured using the equivalent circle diameter of the crystal particles as the particle diameter. For each sample, the particle size of 300 crystal particles was measured, and the average value was calculated as the average particle size.
  • High temperature load life test The high temperature load life test was conducted as follows. A DC voltage was applied to the multilayer ceramic capacitor according to each sample at a temperature of 125 ° C. so that the electric field strengths were 6.3 kV / mm and 12.6 kV / mm. Then, a high temperature load life test was performed on 100 samples, and a sample with an insulation resistance value of 100 k ⁇ or less was determined to be defective before 1000 hours passed, and the number of defects in 100 samples was determined.
  • Table 2 shows the average particle diameter, the dielectric layer thickness, and the number of defects after the high temperature load life test.
  • Sample Nos. 1, 10, and 14 are mainly composed of (Ba, Re) (Ti, M) O 3 , and have good reliability in both DC voltages of 6.3 kV / ⁇ m and 12.6 kV / ⁇ m. showed that.
  • Sample numbers 2 to 9, 11 to 13, and 15 to 17 are mainly composed of (Ba, Ca, Re) (Ti, M) O 3 , and have DC voltages of 6.3 kV / ⁇ m and 12.6 kV / ⁇ m. Both showed good reliability.
  • Sample Nos. 1 to 3, 5, 7, 8, 10 to 14 and 16 have an average particle diameter of 20 nm or more and less than 100 nm, and no defects occur even under test conditions with a DC voltage of 12.6 kV / ⁇ m. It showed good reliability.
  • Sample No. 18 had an average particle size of less than 20 nm, which was a result of low reliability.
  • Sample No. 19 had an average particle size larger than 150 nm and low reliability. In Sample No. 19, the average particle size is large, and it is considered that local electric field concentration occurred in the laminate.
  • Specimen No. 20 was a result with low reliability. This is presumably because the Ca content x is larger than 0.02, it is difficult to densify, and the mechanical strength is inferior.
  • Sample No. 21 had a Re amount y smaller than 0.002 and low reliability. Sample No. 22 also showed low reliability. This is presumably because the Re amount y was larger than 0.1 and segregation occurred after firing.

Abstract

　誘電体層がより一層薄層化されても、高温負荷試験の寿命特性の優れた積層セラミックコンデンサを提供する。　積層セラミックコンデンサ１の誘電体層２を構成する誘電体セラミックとして、一般式（Ｂａ1-x-yＣａxＲｅy）（Ｔｉ1-zＭz）Ｏ3（但し、ＲｅはＬａ、Ｃｅ、Ｐｒ、Ｎｄ、Ｓｍ、Ｅｕ、Ｇｄ、Ｔｂ、Ｄｙ、Ｈｏ、Ｅｒ、Ｔｍ、Ｙｂ、Ｌｕ及びＹの中から選択された少なくとも一種以上の元素、ＭはＭｇ、Ｍｎ、Ａｌ、Ｃｒ及びＺｎの中から選択された少なくとも一種以上の元素）で表されると共に、０≦ｘ≦０．２、０．００２≦ｙ≦０．１、０．００１≦ｚ≦０．０５の範囲である化合物を主成分として含むものを用いる。この誘電体セラミックは、結晶粒子の平均粒径が２０ｎｍ以上かつ１５０ｎｍ以下である。

Description

誘電体セラミック、積層セラミックコンデンサ、及びこれらの製造方法
　本発明は誘電体セラミック及びその製造方法に関する。また、この誘電体セラミックを用いて構成される積層セラミックコンデンサ及びその製造方法に関するものである。
　近年のエレクトロニクス技術の進展に伴い、積層セラミックコンデンサには小型化かつ大容量化が要求されている。これらの要求を満たすため、積層セラミックコンデンサの誘電体層の薄層化が進められている。しかし、誘電体層を薄層化すると、１層あたりに加わる電界強度が相対的に高くなる。よって、誘電体層に用いられる誘電体セラミックに対しては、電圧印加時における信頼性、特に高温負荷試験の寿命特性の向上が求められる。
　例えば、特許文献１には、チタン酸バリウムを主成分とし、副成分として希土類元素、マグネシウム及びマンガンを含むペロブスカイト型の結晶構造を有し、組成式（Ｂａ1-yＲＥy）（Ｔｉ1-a-bＭｇaoＭｎb）Ｏ3（ＲＥ：希土類元素）で表され、各々の範囲が０．０６≦ｙ≦０．０９、０．０３≦ａｏ≦０．０４５、０．０１２≦ｂ≦０．０１８で表されることを特徴とする誘電体セラミックが記載されている。
特開２００７－１４５６４９号公報
　ところが、特許文献１には誘電体層を薄層化した場合についての記載がない。したがって、特許文献１に記載の誘電体セラミックが、誘電体層の厚みを１μｍ程度にまで薄層化した場合に、電圧印加時における信頼性が高いかどうかは不明である。
　本発明はかかる課題に鑑みてなされたものであって、誘電体層がより一層薄層化し、高電界強度の電圧が印加されても、良好な誘電特性を有し、高温負荷試験の寿命特性の優れた積層セラミックコンデンサを提供することを目的とする。
　本発明に係る誘電体セラミックは、一般式（Ｂａ1-x-yＣａxＲｅy）（Ｔｉ1-zＭz）Ｏ3（但し、ＲｅはＬａ、Ｃｅ、Ｐｒ、Ｎｄ、Ｓｍ、Ｅｕ、Ｇｄ、Ｔｂ、Ｄｙ、Ｈｏ、Ｅｒ、Ｔｍ、Ｙｂ、Ｌｕ及びＹの中から選択された少なくとも一種以上の元素、ＭはＭｇ、Ｍｎ、Ａｌ、Ｃｒ及びＺｎの中から選択された少なくとも一種以上の元素）で表されると共に、０≦ｘ≦０．２、０．００２≦ｙ≦０．１、０．００１≦ｚ≦０．０５の範囲である化合物を主成分として含み、結晶粒子の平均粒径が２０ｎｍ以上かつ１５０ｎｍ以下であることを特徴としている。
　また、本発明に係る誘電体セラミックは、平均粒径が２０ｎｍ以上かつ１００ｎｍ未満であることが好ましい。
　また、本発明は、積層されている複数の誘電体層と、誘電体層間の界面に沿って形成されている複数の内部電極と、を有する積層体と、積層体の外表面に形成され、内部電極と電気的に接続されている複数の外部電極と、を備える積層セラミックコンデンサにおいて、誘電体層は、上記の誘電体セラミックからなることを特徴とする積層セラミックコンデンサにも向けられる。
　また、本発明は、一般式（Ｂａ1-x-yＣａxＲｅy）（Ｔｉ1-zＭz）Ｏ3（但し、ＲｅはＬａ、Ｃｅ、Ｐｒ、Ｎｄ、Ｓｍ、Ｅｕ、Ｇｄ、Ｔｂ、Ｄｙ、Ｈｏ、Ｅｒ、Ｔｍ、Ｙｂ、Ｌｕ及びＹの中から選択された少なくとも一種以上の元素、ＭはＭｇ、Ｍｎ、Ａｌ、Ｃｒ及びＺｎの中から選択された少なくとも一種以上の元素）で表されると共に、０≦ｘ≦０．２、０．００２≦ｙ≦０．１、０．００１≦ｚ≦０．０５の範囲である化合物を主成分として含む、セラミック粉末を用意する工程と、セラミック粉末を成形し、成形体を得る工程と、成形体を焼成し、結晶粒子の平均粒径が２０ｎｍ以上かつ１５０ｎｍ以下である誘電体セラミックを得る工程と、を備える、誘電体セラミックの製造方法にも向けられる。
　また、本発明に係る誘電体セラミックの製造方法では、平均粒径が２０ｎｍ以上かつ１００ｎｍ未満であることが好ましい。
　また、本発明は、上記の誘電体セラミックの製造方法を備えることを特徴とする、積層セラミックコンデンサの製造方法にも向けられる。
　この発明に係る誘電体セラミックによれば、上記のような組成を有しつつ、結晶粒子の粒径を上記のように規定することにより、誘電体層がより一層薄層化し、高電界強度の電圧が印加されても、良好な誘電特性を有し、高温負荷試験の寿命特性の優れた積層セラミックコンデンサを提供することが可能である。
本発明に係る積層セラミックコンデンサの断面図である。
　以下において、本発明を実施するための形態について説明する。
　図１は、本発明に係る積層セラミックコンデンサの断面図である。
　積層セラミックコンデンサ１は、積層体５を備えている。積層体５は、積層されている複数の誘電体層２と、複数の誘電体層２間の界面に沿って形成されている複数の内部電極３及び４と、を備えている。内部電極３及び４の材質としては、例えばＮｉを主成分とするものが挙げられる。
　積層体５の外表面上の互いに異なる位置には、外部電極６及び７が形成されている。外部電極６及び７の材質としては、例えばＡｇ又はＣｕを主成分とするものが挙げられる。図１に示した積層セラミックコンデンサでは、外部電極６及び７は、積層体５の互いに対向する各端面上に形成されている。内部電極３及び４は、それぞれ外部電極６及び７と電気的に接続されている。そして、内部電極３及び４は、積層体５の内部において誘電体層２を介して交互に積層されている。
　なお、積層セラミックコンデンサ１は、２個の外部電極６及び７を備える２端子型のものであっても、多数の外部電極を備える他端子型のものであっても良い。
　誘電体層２は、一般式（Ｂａ1-x-yＣａxＲｅy）（Ｔｉ1-zＭz）Ｏ3（但し、ＲｅはＬａ、Ｃｅ、Ｐｒ、Ｎｄ、Ｓｍ、Ｅｕ、Ｇｄ、Ｔｂ、Ｄｙ、Ｈｏ、Ｅｒ、Ｔｍ、Ｙｂ、Ｌｕ及びＹの中から選択された少なくとも一種以上の元素、ＭはＭｇ、Ｍｎ、Ａｌ、Ｃｒ及びＺｎの中から選択された少なくとも一種以上の元素）で表されると共に、０≦ｘ≦０．２、０．００２≦ｙ≦０．１、０．００１≦ｚ≦０．０５の範囲である化合物を主成分として含む誘電体セラミックで構成されている。そして、誘電体セラミックの結晶粒子の平均粒径は２０ｎｍ以上かつ１５０ｎｍ以下となるようにされる。
　また、平均粒径が２０ｎｍ以上かつ１００ｎｍ未満である場合には、高温負荷試験の寿命特性のより一層優れた積層セラミックコンデンサを提供することが可能である。
　なお、（Ｂａ，Ｃａ，Ｒｅ）と（Ｔｉ，Ｍ）のモル比は適宜設定され、好ましくは０．９８～１．０５の範囲で選ばれる。
　セラミック粉末は、例えば、固相合成法で作製される。具体的には、まず、主成分の構成元素であるＢａ、Ｃａ、Ｒｅ、Ｔｉ、Ｍをそれぞれ含む酸化物、炭酸物、塩化物、金属有機化合物等の化合物粉末を所定の割合で混合し、仮焼する。なお、固相合成法の他に、水熱合成法や加水分解法等を適用しても良い。
　積層セラミックコンデンサは、例えば、以下のように作製される。上記のようにして得られたセラミック粉末を用いてセラミックスラリーを作製する。そして、シート成形法等でセラミックグリーンシートを成形する。そして、複数枚のセラミックグリーンシートを積層した後圧着して、成形体を得る。そして、成形体を焼成する。この焼成する工程で、セラミック粉末が焼成され、誘電体セラミックで構成される誘電体層が得られる。その後、積層体の端面に外部電極を焼き付け等で形成する。
　次に、この発明に基づいて実施した実験例について説明する。
　［実験例１］
　（Ａ）セラミック粉末の作製
　出発原料として、微粒のＢａＣＯ3、ＣａＣＯ3、ＴｉＯ2、Ｒｅ（ＲｅはＬａ、Ｃｅ、Ｐｒ、Ｎｄ、Ｓｍ、Ｅｕ、Ｇｄ、Ｔｂ、Ｄｙ、Ｈｏ、Ｅｒ、Ｔｍ、Ｙｂ、Ｌｕ及びＹ）、Ｍ（ＭはＭｇ、Ｍｎ、Ａｌ、Ｃｒ及びＺｎ）の各粉末を用意した。Ｒｅの粉末としては、Ｌａ2Ｏ3、Ｃｅ2Ｏ3、Ｐｒ2Ｏ3、Ｎｄ2Ｏ3、Ｓｍ2Ｏ3、Ｅｕ2Ｏ3、Ｇｄ2Ｏ3、Ｔｂ2Ｏ3、Ｄｙ2Ｏ3、Ｈｏ2Ｏ3、Ｅｒ2Ｏ3、Ｔｍ2Ｏ3、Ｙｂ2Ｏ3、Ｌｕ2Ｏ3及びＹ2Ｏ3の各粉末を用意した。また、Ｍの粉末としては、ＭｇＣＯ3、ＭｎＣＯ3、Ａｌ2Ｏ3、Ｃｒ2Ｏ3、ＺｎＯの各粉末を用意した。そして、これらの粉末を（Ｂａ1-x-yＣａxＲｅy）（Ｔｉ1-zＭz）Ｏ3の表１の組成となるように秤量した後、ボールミルで８０時間混合した。その後、上記の混合粉末を１０００℃の熱処理で仮焼合成することにより、（Ｂａ1-x-yＣａxＲｅy）（Ｔｉ1-zＭz）Ｏ3の主成分粉末を得た。その後、主成分粉末１００モル部に対して、ＢａＣＯ3を１．５モル部、ＳｉＯ2を２モル部添加して、セラミック粉末を得た。
　得られたセラミック粉末の平均粒径は１０ｎｍ程度であった。また、ＸＲＤによると、セラミック粉末における未反応物は検出レベルを下回った。すなわち、このセラミック粉末は、非常に微粒であるにもかかわらず、合成度の高い粉末であることが確認された。
Figure JPOXMLDOC01-appb-T000001
　（Ｂ）積層セラミックコンデンサの作製
　まず、誘電体層となるべきセラミックグリーンシートを形成した。具体的には、上述したセラミック粉末に、ポリビニルブチラール系バインダ及びエタノールを加えて、ボールミルにより２４時間湿式混合した。その後、フィルターでフィルタリングを行い、所定の範囲内の粒径以外の粒径を有する粉末を排除したスラリーを作製した。そして、このスラリーをリップ方式によりシート上に成形して、セラミックグリーンシートを得た。セラミックグリーンシートの厚さは、後述するように、焼成後に表２の「誘電体層厚」に示す厚さになるようにした。
　次に、成形体を作製した。具体的には、特定のセラミックグリーンシート上に、Ｎｉを主成分として含む導電性ペーストをスクリーン印刷し、内部電極となるべき導電性ペースト膜を形成した。そして、導電性ペースト膜が形成されたセラミックグリーンシートを、導電性ペースト膜の引き出されている側が互い違いになるように複数枚を積層した後に圧着して、成形体を得た。
　次に、成形体を焼成した。具体的には、まず、還元雰囲気で３００℃の温度に加熱して、バインダを燃焼させた。その後、酸素分圧が１０-10ＭＰａのＨ2－Ｎ2－Ｈ2Ｏガスからなる還元性雰囲気中にて、１２００℃の温度で１時間焼成した。
　次に、外部電極を形成した。具体的には、積層体の両端面にＢ2Ｏ3－Ｌｉ2Ｏ－ＳｉＯ2－ＢａＯ系ガラスフリットを含有するＣｕペーストを塗布した。その後、窒素雰囲気中で８００℃の温度で加熱して、Ｃｕペーストを焼き付けた。このようにして内部電極と電気的に接続された外部電極を形成した。
　以上のようにして積層セラミックコンデンサを作製した。積層セラミックコンデンサの外形寸法は、長さ１．０ｍｍ、幅０．５ｍｍ、厚さ０．５ｍｍであり、有効誘電体層の層数は１００層であり、誘電体層１層あたりの内部電極の対向面積は０．３ｍｍ2であった。また、内部電極間に介在する誘電体層の厚みは、表２の「誘電体層厚」に示すとおりであった。
　（Ｃ）特性評価
　得られた積層セラミックコンデンサについて、各種特性を評価した。
　［平均粒径］
　平均粒径は以下のように算出した。まず、各試料に係る積層セラミックコンデンサを破断し、１０００℃の温度でサーマルエッチングを行い、破断面を走査型顕微鏡を用いて観察した。そして、この観察像について画像解析を行い、結晶粒子の円相当径を粒径として、結晶粒子の粒径を測定した。そして、各試料につき、３００個の結晶粒子の粒径を測定し、その平均値を平均粒径として算出した。
　［高温負荷寿命試験］
　高温負荷寿命試験は、下記のように実施した。各試料に係る積層セラミックコンデンサに、温度１２５℃にて、６．３ｋＶ／ｍｍ及び１２．６ｋＶ／ｍｍの各電界強度となるようにＤＣ電圧を印加した。そして、１００個の試料で高温負荷寿命試験を実施し、１０００時間経過するまでに、絶縁抵抗値が１００ｋΩ以下になった試料を不良と判定し、試料１００個中の不良個数を求めた。
　表２に、平均粒径、誘電体層厚及び高温負荷寿命試験後の不良個数を示す。
Figure JPOXMLDOC01-appb-T000002
　なお、表１及び表２において、試料番号に*を付したものは、この発明の範囲外の試料である。
　（Ｄ）考察
　試料番号１、１０、１４は（Ｂａ，Ｒｅ）（Ｔｉ，Ｍ）Ｏ3が主成分であり、ＤＣ電圧が６．３ｋＶ／μｍ、１２．６ｋＶ／μｍ共に、良好な信頼性を示した。また、試料番号２～９、１１～１３、１５～１７は（Ｂａ，Ｃａ，Ｒｅ）（Ｔｉ，Ｍ）Ｏ3が主成分であり、ＤＣ電圧が６．３ｋＶ／μｍ、１２．６ｋＶ／μｍ共に、良好な信頼性を示した。なお、試料番号１～３、５、７、８、１０～１４、１６は平均粒径が２０ｎｍ以上かつ１００ｎｍ未満であり、ＤＣ電圧が１２．６ｋＶ／μｍの試験条件でも不良が発生せず、良好な信頼性を示した。
　これらに対して、試料番号１８は平均粒径が２０ｎｍ未満であり、信頼性が低い結果であった。また、試料番号１９は平均粒径が１５０ｎｍより大きく、信頼性が低い結果であった。試料番号１９では、平均粒径が大きく、積層体中で局所的な電界集中が生じたためと考えられる。
　試料番号２０でも信頼性が低い結果であった。これは、Ｃａ量ｘが０．０２より大きく、緻密化しづらくなり、機械的強度が劣ったためと考えられる。
　試料番号２１では、Ｒｅ量ｙが０．００２より小さく、信頼性が低い結果となった。また、試料番号２２でも信頼性が低い結果となった。これは、Ｒｅ量ｙが０．１より大きく、焼成後に偏析が生じたためと考えられる。
　試料番号２３では、Ｍ量ｚが０．００１より小さく、信頼性が低い結果となった。また、試料番号２４でも信頼性が低い結果となった。これは、Ｍ量ｚが０．０５より大きく、焼成後に偏析が生じたためと考えられる。
　［実験例２］
　実験例２では、不純物の影響を評価した。積層セラミックコンデンサの原料作製工程等において、Ｓｒ、Ｚｒ、Ｈｆ、Ｚｎ、Ｎａ、Ａｇ、Ｐｄ及びＮｉ等が不純物として混入する可能性がある。これらは結晶粒子内及び結晶粒子間を占める結晶粒界に存在する可能性がある。また、積層セラミックコンデンサの焼成工程等において、内部電極成分が誘電体セラミック中の結晶粒界及び結晶粒子間を占める結晶粒界に拡散して存在する可能性がある。実験例２は、これらの不純物の影響を評価しようとするものである。
　（Ａ）セラミック粉末の作製
　実験例１の試料番号１３の組成に、表３に示した不純物成分を加えたことを除いて、実験例１と同様の方法でセラミック粉末を作製した。
Figure JPOXMLDOC01-appb-T000003
　（Ｂ）積層セラミックコンデンサの作製
　上記セラミック粉末を用いて、実験例１と同様の方法で積層セラミックコンデンサを作製した。
　（Ｃ）特性評価
　得られた積層セラミックコンデンサについて、実験例１と同様の方法で各種特性を評価した。表４に高温負荷寿命試験の結果を示す。
Figure JPOXMLDOC01-appb-T000004
　（Ｄ）考察
　表４から分かるように、不純物が混入した試料３１～４０のいずれにおいても、電界強度が６．３ｋＶ／ｍｍ及び１２．６ｋＶ／ｍｍの双方において、高温負荷寿命試験での不良個数が０であり、高い信頼性を示した。また、試料３１～４０のいずれにおいても、平均粒径は２０ｎｍ以上かつ１５０ｎｍ以下であった。
　１　積層セラミックコンデンサ
　２　誘電体層
　３、４　内部電極
　５　積層体
　６、７　外部電極

Claims (6)

  1. 　一般式（Ｂａ1-x-yＣａxＲｅy）（Ｔｉ1-zＭz）Ｏ3（但し、ＲｅはＬａ、Ｃｅ、Ｐｒ、Ｎｄ、Ｓｍ、Ｅｕ、Ｇｄ、Ｔｂ、Ｄｙ、Ｈｏ、Ｅｒ、Ｔｍ、Ｙｂ、Ｌｕ及びＹの中から選択された少なくとも一種以上の元素、ＭはＭｇ、Ｍｎ、Ａｌ、Ｃｒ及びＺｎの中から選択された少なくとも一種以上の元素）で表されると共に、０≦ｘ≦０．２、０．００２≦ｙ≦０．１、０．００１≦ｚ≦０．０５の範囲である化合物を主成分として含み、結晶粒子の平均粒径が２０ｎｍ以上かつ１５０ｎｍ以下である誘電体セラミック。
  2. 　前記平均粒径が２０ｎｍ以上かつ１００ｎｍ未満である、請求項１に記載の誘電体セラミック。
  3. 　積層されている複数の誘電体層と、前記誘電体層間の界面に沿って形成されている複数の内部電極と、を有する積層体と、前記積層体の外表面に形成され、前記内部電極と電気的に接続されている複数の外部電極と、を備える積層セラミックコンデンサにおいて、
    　前記誘電体層は、請求項１または２に記載の誘電体セラミックからなることを特徴とする積層セラミックコンデンサ。
  4. 　一般式（Ｂａ1-x-yＣａxＲｅy）（Ｔｉ1-zＭz）Ｏ3（但し、ＲｅはＬａ、Ｃｅ、Ｐｒ、Ｎｄ、Ｓｍ、Ｅｕ、Ｇｄ、Ｔｂ、Ｄｙ、Ｈｏ、Ｅｒ、Ｔｍ、Ｙｂ、Ｌｕ及びＹの中から選択された少なくとも一種以上の元素、ＭはＭｇ、Ｍｎ、Ａｌ、Ｃｒ及びＺｎの中から選択された少なくとも一種以上の元素）で表されると共に、０≦ｘ≦０．２、０．００２≦ｙ≦０．１、０．００１≦ｚ≦０．０５の範囲である化合物を主成分として含む、セラミック粉末を用意する工程と、
    　前記セラミック粉末を成形し、成形体を得る工程と、
    　前記成形体を焼成し、結晶粒子の平均粒径が２０ｎｍ以上かつ１５０ｎｍ以下である誘電体セラミックを得る工程と、
    を備える、誘電体セラミックの製造方法。
  5. 　前記平均粒径が２０ｎｍ以上かつ１００ｎｍ未満である、請求項４に記載の誘電体セラミックの製造方法。
  6. 　請求項４または５の誘電体セラミックの製造方法を備えることを特徴とする、積層セラミックコンデンサの製造方法。
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JP5733313B2 (ja) 2015-06-10
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