JP2018528914A - 誘電体組成物、誘電体素子、電子部品および積層電子部品 - Google Patents
誘電体組成物、誘電体素子、電子部品および積層電子部品 Download PDFInfo
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- JP2018528914A JP2018528914A JP2018501915A JP2018501915A JP2018528914A JP 2018528914 A JP2018528914 A JP 2018528914A JP 2018501915 A JP2018501915 A JP 2018501915A JP 2018501915 A JP2018501915 A JP 2018501915A JP 2018528914 A JP2018528914 A JP 2018528914A
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Abstract
【解決手段】 少なくともBi、Na、SrおよびTiを含むペロブスカイト型の結晶構造を有する粒子を含む誘電体組成物である。誘電体組成物は、Tiを100モル部として、La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Yb、Ba、Ca、Mg、およびZnの中から選ばれる少なくとも1種以上を0.5モル部以上、11.1モル部以下含む。Srに対するBiのモル比率をαとした場合に、0.17≦α≦2.83である。粒子のうち少なくとも一部は、誘電体組成物全体の平均Bi濃度に対して1.2倍以上のBi濃度である高Bi相を含む。粒子内にある高Bi相の面積の合計が粒子の面積の合計に対して0.1%以上15%以下である。
【選択図】図3
Description
少なくともBi、Na、SrおよびTiを含むペロブスカイト型の結晶構造を有する粒子を含む誘電体組成物であって、
前記誘電体組成物は、La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Yb、Ba、Ca、Mg、およびZnの中から選ばれる少なくとも1種以上を含み、
前記誘電体組成物におけるTiの含有量を100モル部として、前記La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Yb、Ba、Ca、Mg、およびZnの中から選ばれる少なくとも1種以上の含有量が0.5モル部以上、11.1モル部以下であり、
前記誘電体組成物における前記Srに対する前記Biのモル比率をαとした場合に、0.17≦α≦2.83であり、
前記粒子のうち少なくとも一部は、前記誘電体組成物全体の平均Bi濃度に対して1.2倍以上のBi濃度である高Bi相を含み、
前記誘電体組成物の切断面において、前記粒子内にある前記高Bi相の面積の合計が前記粒子の面積の合計に対して0.1%以上15%以下であることを特徴とする。
出発原料として、酸化ビスマス(Bi2O3)、炭酸ナトリウム(Na2CO3)、炭酸ストロンチウム(SrCO3)、炭酸バリウム(BaCO3)、炭酸カルシウム(CaCO3)、炭酸マグネシウム(MgCO3)、酸化亜鉛(ZnO)、水酸化ランタン(La(OH)3)、酸化ネオジウム(Nd2O3)、酸化サマリウム(Sm2O3)、酸化ガドリニウム(Gd2O3)、酸化チタン(TiO2)を準備した。
なお、前記積層セラミック焼成体の誘電体層を溶剤により溶解し、ICP発光分光分析したところ、副成分の含有量、Srに対するBiのモル比率αなど、前記誘電体層の組成は表1に示した組成と同一の組成であることが確認された。
前記100個の粒子において、高Bi相(第1相)が占める面積をS1、高Bi相以外の部分(第2相)が占める面積をS2、粒子全体の面積をS3とした場合に、S1+S2=S3が成り立つ。それぞれの領域を選択し、それぞれの領域を占めるピクセルの個数をカウントし、1ピクセルあたりの面積を掛けることでS1、S2およびS3を算出した。下記式(1)より、粒子全体の面積S3に対する高Bi相の面積S1の割合(%)を算出した。
(S1/S3)×100 ・・・ 式(1)
前記100個の粒子に含まれる第1相の組成分析を行った。1つの第1相に対し、測定点を10点以上設定した。前記1つの第1相において、各測定点におけるBi濃度(原子濃度)の平均値を、当該測定点が含まれる前記1つの第1相の面積で掛けることで、当該第1相に含まれるBiの含有量を算出した。そして、前記100個の粒子に含まれる各第1相に対して、Biの含有量を算出し、各第1相におけるBiの含有量を合計することで、第1相に含まれるBiの含有量の合計を算出した。
得られた積層セラミックコンデンサの比誘電率ε1は、デジタルLCRメータ(Hewlett−Packard社,4284A)を使用し、室温25℃、周波数1kHz、入力信号レベル(測定電圧)1.0Vrmsの条件から測定された静電容量と積層セラミックコンデンサの電極間距離、電極の有効面積から算出した(単位なし)。
比誘電率ε2は、DCバイアス発生装置(GLASSMAN HIGH VOLTAGE社,WX10P90)をデジタルLCRメータ(Hewlett−Packard社,4284A)に接続して、評価用試料に5V/μmのDCバイアスを印加しながら、室温25℃、周波数1kHz、入力信号レベル(測定電圧)1.0Vrmsの条件から測定された静電容量、有効電極面積および電極間距離から算出した(単位なし)。比誘電率ε2は高い方が好ましく、本実施例では1000以上を良好とし、1300以上をさらに良好とした。
DCバイアス特性は、比誘電率ε1と比誘電率ε2を用い、下の式(2)より算出した。DCバイアス特性の絶対値は小さい方が好ましく、本実施例では−20%〜+20%を良好とし、−15%〜+15%をさらに良好とした。
DCバイアス特性(%)=100×(ε2−ε1)/ε1 ・・・ 式(2)
高温負荷寿命は、恒温槽及びデジタル超高抵抗計(ADVANTEST社、R8340A)を使用し、150℃にて、50V/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、この評価は10個のコンデンサ試料について行い、その平均を高温負荷寿命とした。本実施例では20時間以上を良好とし、25時間以上をさらに良好とした。
また、抗折強度の測定方法については、以下に詳細に説明する。
2,3…電極
5…積層体
6A,6B…内部電極層
7…誘電体層
11A,11B…端子電極
8…第1相(粒子内の高Bi相)
9…第2相(粒子内であって高Bi相以外の部分)
10…粒界
20…高Bi相を含まない焼結体粒子
30…高Bi相を含む焼結体粒子
40…高Bi相のみからなる焼結体粒子
100…セラミックコンデンサ
200…積層セラミックコンデンサ
300…誘電体組成物
Claims (5)
- 少なくともBi、Na、SrおよびTiを含むペロブスカイト型の結晶構造を有する粒子を含む誘電体組成物であって、
前記誘電体組成物は、La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Yb、Ba、Ca、Mg、およびZnの中から選ばれる少なくとも1種以上を含み、
前記誘電体組成物におけるTiの含有量を100モル部として、前記La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Yb、Ba、Ca、Mg、およびZnの中から選ばれる少なくとも1種以上の含有量が0.5モル部以上、11.1モル部以下であり、
前記誘電体組成物における前記Srに対する前記Biのモル比率をαとした場合に、0.17≦α≦2.83であり、
前記粒子のうち少なくとも一部は、前記誘電体組成物全体の平均Bi濃度に対して1.2倍以上のBi濃度である高Bi相を含み、
前記誘電体組成物の切断面において、前記粒子内にある前記高Bi相の面積の合計が前記粒子の面積の合計に対して0.1%以上15%以下であることを特徴とする誘電体組成物。 - 前記粒子内にある前記高Bi相に含まれるBiの含有量の合計は、前記粒子内であって前記高Bi相以外の部分に含まれるBiの含有量の合計に対して、原子比で1.15倍以上2.15倍以下である請求項1に記載の誘電体組成物。
- 請求項1および2のいずれかに記載の誘電体組成物を備える誘電体素子。
- 請求項1および2のいずれかに記載の誘電体組成物からなる誘電体層を備える電子部品。
- 請求項1および2のいずれかに記載の誘電体組成物からなる誘電体層と内部電極層とを交互に積層されてなる積層部分を有する積層電子部品。
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