JP2009084110A - 誘電体磁器組成物および電子部品 - Google Patents
誘電体磁器組成物および電子部品 Download PDFInfo
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- JP2009084110A JP2009084110A JP2007255598A JP2007255598A JP2009084110A JP 2009084110 A JP2009084110 A JP 2009084110A JP 2007255598 A JP2007255598 A JP 2007255598A JP 2007255598 A JP2007255598 A JP 2007255598A JP 2009084110 A JP2009084110 A JP 2009084110A
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Abstract
【解決手段】BaTiO3と、BaZrO3と、R酸化物(Rは希土類元素)とを有する誘電体磁器組成物であって、BaTiO3 100モルに対して、BaZrO3の含有量をAモル、R酸化物の含有量をCモルとした場合に、40≦A≦65モル、4≦C≦15モルで、かつ、式(1)および(2)を同時に満足する誘電体磁器組成物。式(1)…0.0038A−0.147≦B≦0.004A+0.04(Bは、BaTiO3のX線最大ピーク強度に対するBaZrO3のX線最大ピーク強度の比)、式(2)…0.0041C−0.0115≦D≦0.0046C+0.084(Dは、BaTiO3のX線最大ピーク強度に対するR酸化物のX線最大ピーク強度の比)
【選択図】なし
Description
Bam TiO2+m (ただし、mは、0.99≦m≦1.01)と、
Ban ZrO2+n (ただし、nは、0.99≦n≦1.01)と、
Rの酸化物(ただし、Rは、Sc、Y、La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、YbおよびLuから選択される少なくとも1種)と、を有する誘電体磁器組成物であって、
前記Bam TiO2+m 100モルに対して、前記Ban ZrO2+nの含有量をAモル、前記Rの酸化物の含有量をCモルとした場合に、前記Aが、Ban ZrO2+n 換算で、40≦A≦65モル、前記Cが、R2 O3 換算で、4≦C≦15モルであり、かつ、下記式(1)および(2)を同時に満足することを特徴とする。
式(1)…0.0038A−0.147≦B≦0.004A+0.04(ただし、Bは、前記Bam TiO2+mのX線最大ピーク強度に対する前記Ban ZrO2+nのX線最大ピーク強度の比である)
式(2)…0.0041C−0.0115≦D≦0.0046C+0.084(ただし、Dは、前記Bam TiO2+mのX線最大ピーク強度に対する前記Rの酸化物のX線最大ピーク強度の比である)
前記Bam TiO2+m 100モルに対して、各成分の酸化物または複合酸化物換算での比率が、
Mgの酸化物:4〜12モル、
Mn、Cr、CoおよびFeの酸化物:0.5〜3モル、
Si、Li、Al、GeおよびBの酸化物:3〜9モルである。
図1は本発明の一実施形態に係る積層セラミックコンデンサの断面図、
図2はBaTiO3、BaZrO3およびGd2O3のX線最大ピーク強度を示すX線回折チャート図、
図3はBaZrO3の含有量(A)と、BaTiO3のX線最大ピーク強度に対するBaZrO3のX線最大ピーク強度の比(B)と、の関係を示すグラフであり、
図4はGd2O3の含有量(C)と、BaTiO3のX線最大ピーク強度に対するGd2O3のX線最大ピーク強度の比(D)と、の関係を示すグラフである。
図1に示すように、本発明の一実施形態に係る積層セラミックコンデンサ1は、誘電体層2と内部電極層3とが交互に積層された構成のコンデンサ素子本体10を有する。このコンデンサ素子本体10の両端部には、素子本体10の内部で交互に配置された内部電極層3と各々導通する一対の外部電極4が形成してある。コンデンサ素子本体10の形状に特に制限はないが、通常、直方体状とされる。また、その寸法にも特に制限はなく、用途に応じて適当な寸法とすればよい。
誘電体層2は、本発明の誘電体磁器組成物を含有する。
本発明の誘電体磁器組成物は、少なくとも、Bam TiO2+m (ただし、mは、0.99≦m≦1.01)と、Ban ZrO2+n (ただし、nは、0.99≦n≦1.01)と、Rの酸化物(ただし、Rは、Sc、Y、La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、YbおよびLuから選択される少なくとも1種)と、を有する。この際、酸素(O)量は、上記式の化学量論組成から若干偏倚してもよい。
式(1)…0.0038A−0.147≦B≦0.004A+0.04
式(2)…0.0041C−0.0115≦D≦0.0046C+0.084
内部電極層3に含有される導電材は特に限定されないが、誘電体層2の構成材料が耐還元性を有するため、比較的安価な卑金属を用いることができる。導電材として用いる卑金属としては、NiまたはNi合金が好ましい。Ni合金としては、Mn,Cr,CoおよびAlから選択される1種以上の元素とNiとの合金が好ましく、合金中のNi含有量は95重量%以上であることが好ましい。なお、NiまたはNi合金中には、P等の各種微量成分が0.1重量%程度以下含まれていてもよい。また、内部電極層3は、市販の電極用ペーストを使用して形成してもよい。内部電極層3の厚さは用途等に応じて適宜決定すればよい。
外部電極4に含有される導電材は特に限定されないが、本発明では安価なNi,Cuや、これらの合金を用いることができる。外部電極4の厚さは用途等に応じて適宜決定すればよい。
本実施形態の積層セラミックコンデンサ1は、従来の積層セラミックコンデンサと同様に、ペーストを用いた通常の印刷法やシート法によりグリーンチップを作製し、これを焼成した後、外部電極を印刷または転写して焼成することにより製造される。以下、製造方法について具体的に説明する。
まず、BaTiO3(m=1.000)、BaZrO3(n=1.000) 、MgCO3 、Gd2 O3 、MnO、およびSiO2 を準備した。誘電体原料は、以下の2種類の方法により準備した。第1の方法としては、まず、BaZrO3、MgCO3 、Gd2 O3 、MnO、およびSiO2をボールミルで混合し、得られた混合粉を1000℃で予め仮焼して、平均粒子径0.2μmの焙焼粉を調製した。次いで、得られた焙焼粉に、BaTiO3を加えて、ボールミルで15時間、湿式粉砕し、乾燥して、平均粒径0.15μmの誘電体原料を得た。
第2の方法としては、予め、BaTiO3およびBaZrO3をボールミルにて混合し、得られた混合粉を1000℃で予め仮焼して、平均粒子径0.2μmの焙焼粉を調製した。この焙焼粉においては、BaZrO3がBaTiO3に完全に固溶している。次いで、得られた焙焼粉に、MgCO3 、Gd2 O3 、MnO、およびSiO2 を加えて、ボールミルで15時間、湿式粉砕し、乾燥して、平均粒径0.15μmの誘電体原料を得た。
なお、いずれの方法であっても、MgCO3 は、焼成後には、MgOとして誘電体磁器組成物中に含有されることとなる。
なお、BaTiO3 100モルに対して、MgCO3成分の添加量は8モル、MnO成分の添加量は1.5モル、SiO2成分の添加量は4.5モルであった。
X線回折は、X線源にCu−Kα線を用い、その測定条件は、電圧50kV、電流300mAで、2θ=10°〜80°の範囲を、走査速度1/16 deg/min、積算時間1secであった。得られたX線回折チャートからBaTiO3、BaZrO3およびGd2O3の最大ピークを同定し、BaTiO3のX線最大ピーク強度に対するBaZrO3のX線最大ピーク強度の比(B)と、BaTiO3のX線最大ピーク強度に対するGd2O3のX線最大ピーク強度の比(D)と、を求めた。たとえば、図2に示す2θ=27°〜35°の範囲におけるX線回折チャートにおいて、BaTiO3の最大X線ピーク強度を1とする。そうすると、このときのBaZrO3のX線最大ピーク強度は0.08、Gd2O3のX線最大ピーク強度は0.03と求められる。すなわち、Bが0.08、Dが0.03である。得られたピーク強度比の結果を表1に示す。また、BaZrO3の含有量(A)とピーク強度比(B)との関係を示すグラフを図3に示す。
コンデンサ試料に対し、基準温度25℃において、デジタルLCRメータ(YHP社製4284A)にて、周波数1kHz、入力信号レベル(測定電圧)1Vrmsの信号を入力し、静電容量Cを測定した。そして、比誘電率εs(単位なし)を、誘電体層の厚みと、有効電極面積と、測定の結果得られた静電容量Cとに基づき算出した。比誘電率は高いほうが好ましく、本実施例では、250以上を良好とした。結果を表1に示す。
コンデンサ試料に対し、125℃において、デジタルLCRメータ(YHP社製4284A)にて、周波数1kHz、入力信号レベル(測定電圧)1Vrmsの条件で静電容量を測定し、基準温度25℃における静電容量に対する変化率を算出した。本実施例では、±15%以内を良好とした。結果を表1に示す。
コンデンサ試料に対し、25℃にて、10V/μmの電界下で直流電圧の印可状態に保持し、容量変化率を算出した。本実施例では、−10%以上を良好とした。結果を表1に示す。
コンデンサ試料に対し、200℃にて、40V/μmの電界下で直流電圧の印加状態に保持し、寿命時間を測定することにより、高温加速寿命(HALT)を評価した。本実施例においては、印加開始から絶縁抵抗が一桁落ちるまでの時間を寿命と定義した。また、この高温加速寿命は、10個のコンデンサ試料について行った。本実施例では、20時間以上を良好とした。結果を表1に示す。
コンデンサ試料に対し、温度25℃において、直流電圧を昇温速度100V/sec.で印加し、10mAの電流が流れた時の誘電体層厚みに対する電圧値(単位:V/μm)を破壊電圧とし、破壊電圧を測定することにより、コンデンサ試料の耐圧を評価した。本実施例では、破壊電圧50V/μm以上を良好とした。結果を表1に示す。
まず、コンデンサ試料を、所定パターンの電極がプリントしてあるガラスエポキシ基板にハンダ付けすることにより固定した。次いで、基板に固定したコンデンサ試料に対して、AC:10Vrms/μm、周波数3kHzの条件で電圧を印加し、電圧印加時におけるコンデンサ試料表面の振動幅を測定し、これを電歪量とした。なお、コンデンサ試料表面の振動幅の測定には、レーザードップラー振動計を使用した。また、本実施例では、10個のコンデンサ試料を用いて測定した値の平均値を電歪量とした。電歪量は低いほうが好ましく、本実施例では、10ppm未満を良好とした。結果を表1に示す。
これに対して、上記の(A)〜(D)のいずれか1つでも本発明の範囲外である場合には、高温負荷寿命が悪化する結果となった。たとえば、試料番号2および7では、BaZrO3がBaTiO3に完全に固溶しており、未固溶のBaZrO3が存在していないため、Bが0となってしまい、高温負荷寿命が悪化していることが確認できる。なお、図3においては、本発明の範囲を斜線で表し、表1の実施例を黒丸、比較例を白三角で示してある。
誘電体原料の組成は、Gd2O3の含有量(C)を表2に示す量とした以外は、試料番号10と同様にした。試料番号20、22〜25、27〜37では、上記の第1の方法により調製した誘電体原料を用いた。
また、試料番号21および26では、以下の第3の方法により調製した誘電体原料を用いた。第3の方法としては、予め、BaTiO3およびGd2O3をボールミルにて混合し、得られた混合粉を1000℃で予め仮焼して、平均粒子径0.2μmの焙焼粉を調製した。すなわち、Gd2O3がBaTiO3に完全に固溶している。次いで、得られた焙焼粉に、BaZrO3、MgCO3 、MnO、およびSiO2 を加えて、ボールミルで15時間、湿式粉砕し、乾燥して、誘電体原料を得た。
得られた誘電体原料から、実施例1と同様にして、積層セラミックコンデンサを製造し、実施例1と同様の評価を行った。結果を表2に示す。また、Gd2O3の含有量(C)とピーク強度比(D)との関係を示すグラフを図4に示す。
これに対して、上記の(A)〜(D)のいずれか1つでも本発明の範囲外である場合には、高温負荷寿命が悪化する結果となった。実施例1と同様に、試料番号21および26では、Dが0となり、高温負荷寿命が悪化していることが確認できる。なお、図4においては、本発明の範囲を斜線で表し、表2の実施例を黒丸、比較例を白三角とした。
10… コンデンサ素子本体
2… 誘電体層
3… 内部電極層
4… 外部電極
Claims (3)
- Bam TiO2+m (ただし、mは、0.99≦m≦1.01)と、
Ban ZrO2+n (ただし、nは、0.99≦n≦1.01)と、
Rの酸化物(ただし、Rは、Sc、Y、La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、YbおよびLuから選択される少なくとも1種)と、を有する誘電体磁器組成物であって、
前記Bam TiO2+m 100モルに対して、前記Ban ZrO2+nの含有量をAモル、前記Rの酸化物の含有量をCモルとした場合に、前記Aが、Ban ZrO2+n 換算で、40≦A≦65モル、前記Cが、R2 O3 換算で、4≦C≦15モルであり、かつ、下記式(1)および(2)を同時に満足することを特徴とする誘電体磁器組成物。
式(1)…0.0038A−0.147≦B≦0.004A+0.04(ただし、Bは、前記Bam TiO2+mのX線最大ピーク強度に対する前記Ban ZrO2+nのX線最大ピーク強度の比である)
式(2)…0.0041C−0.0115≦D≦0.0046C+0.084(ただし、Dは、前記Bam TiO2+mのX線最大ピーク強度に対する前記Rの酸化物のX線最大ピーク強度の比である) - Mgの酸化物と、Mn、Cr、CoおよびFeから選ばれる少なくとも1種の酸化物と、Si、Li、Al、GeおよびBから選ばれる少なくとも1種の酸化物と、をさらに有し、
前記Bam TiO2+m 100モルに対して、各成分の酸化物または複合酸化物換算での比率が、
Mgの酸化物:4〜12モル、
Mn、Cr、CoおよびFeの酸化物:0.5〜3モル、
Si、Li、Al、GeおよびBの酸化物:3〜9モル、
である請求項1に記載の誘電体磁器組成物。 - 請求項1または2に記載の誘電体磁器組成物からなる誘電体層と、内部電極層と、を有する電子部品。
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007255598A JP4967963B2 (ja) | 2007-09-28 | 2007-09-28 | 誘電体磁器組成物および電子部品 |
| TW097134838A TW200929283A (en) | 2007-09-28 | 2008-09-11 | Dielectric ceramic compositions and electronic components |
| US12/232,875 US7790645B2 (en) | 2007-09-28 | 2008-09-25 | Dielectric ceramic composition and an electric device |
| KR1020080094049A KR100979857B1 (ko) | 2007-09-28 | 2008-09-25 | 유전체 자기 조성물 및 전자 부품 |
| CN2008101769256A CN101407417B (zh) | 2007-09-28 | 2008-09-28 | 电介质陶瓷组合物及电子部件 |
| EP08165396A EP2045221A3 (en) | 2007-09-28 | 2008-09-29 | A dielectric ceramic composition and an electric device |
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| EP (1) | EP2045221A3 (ja) |
| JP (1) | JP4967963B2 (ja) |
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| JP2012001378A (ja) * | 2010-06-14 | 2012-01-05 | Tdk Corp | 誘電体磁器組成物およびその製造方法 |
| CN106348753A (zh) * | 2015-07-16 | 2017-01-25 | 台北科技大学 | 陶瓷电容介电材料 |
| JP2017024969A (ja) * | 2015-07-16 | 2017-02-02 | 国立臺北科技大學 | セラミックコンデンサ誘電体材料 |
| CN106348753B (zh) * | 2015-07-16 | 2019-12-13 | 台北科技大学 | 陶瓷电容介电材料 |
Also Published As
| Publication number | Publication date |
|---|---|
| EP2045221A3 (en) | 2011-07-06 |
| CN101407417A (zh) | 2009-04-15 |
| US7790645B2 (en) | 2010-09-07 |
| TW200929283A (en) | 2009-07-01 |
| CN101407417B (zh) | 2012-01-04 |
| KR100979857B1 (ko) | 2010-09-02 |
| US20090088315A1 (en) | 2009-04-02 |
| JP4967963B2 (ja) | 2012-07-04 |
| EP2045221A2 (en) | 2009-04-08 |
| KR20090033039A (ko) | 2009-04-01 |
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