TWI441791B - 介電質陶瓷及積層陶瓷電容器 - Google Patents

介電質陶瓷及積層陶瓷電容器 Download PDF

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TWI441791B
TWI441791B TW100106524A TW100106524A TWI441791B TW I441791 B TWI441791 B TW I441791B TW 100106524 A TW100106524 A TW 100106524A TW 100106524 A TW100106524 A TW 100106524A TW I441791 B TWI441791 B TW I441791B
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dielectric ceramic
ceramic
capacitor
dielectric
main component
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TW201204676A (en
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Megumi Fukuda
Takayuki Yao
Makoto Matsuda
Taisuke Kanzaki
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Murata Manufacturing Co
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Description

介電質陶瓷及積層陶瓷電容器
本發明係關於一種介電質陶瓷及積層陶瓷電容器，尤其是關於一種適合於薄層大容量型之積層陶瓷電容器中使用之介電質陶瓷及使用該介電質陶瓷而構成之積層陶瓷電容器。
作為滿足積層陶瓷電容器之小型化且大容量化之要求的有效方法之一，有時謀求積層陶瓷電容器中所包含之介電質陶瓷層之薄層化。因此，最近要求介電質陶瓷層之厚度變薄至例如未達1 μm。然而，隨著介電質陶瓷層之薄層化不斷推進，施加於介電質陶瓷層之每層之電場強度相對變高。因此，對於所使用之介電質陶瓷，要求電壓施加時之可靠性之提高，更特定而言，尤其要求高溫負荷試驗中之壽命特性之提高。
為謀求上述可靠性之提高，已知有效之方法為藉由使介電質陶瓷中之結晶粒子之晶界增多而增加晶界面積。為增加晶界面積，必需減小結晶粒子之粒徑。
作為本發明所感興趣之介電質陶瓷，例如有日本專利特開2005-145791號公報(專利文獻1)中所記載者。
專利文獻1中記載有藉由包括焙燒主成分原料及副成分原料之步驟之製造方法而製造的介電質陶瓷組合物。更詳細而言，記載有一種利用下述方法而製造之介電質陶瓷組合物，即，作為焙燒前之主成分原料，而使用ABO3 所表示之鈣鈦礦型結晶結構之鈦酸鋇原料粉末，且A部位成分和B部位成分之比A/B以莫耳比計為1.006≦A/B≦1.035，比表面積為8~50 m2 /g。
根據專利文獻1，上述介電質陶瓷組合物為用作積層陶瓷電容器之介電質陶瓷層者，由微細之粒子所構成，且即便於將電容器薄層化之情形時，可靠性仍較高，具有良好之溫度特性，高溫負荷壽命特性優異。
然而，於專利文獻1所記載之實施例中，如其表1及表3所示，僅揭示有厚度為2.3~2.6 μm之範圍之介電質陶瓷層。再者，作為介電質陶瓷之燒結體中之結晶粒子之平均粒徑，於上述表1及表3中，揭示有0.141~0.284 μm之範圍之數值。
即，於專利文獻1中未記載任何關於介電質陶瓷層之厚度未達1 μm之情形。因此，尚不明確專利文獻1中所記載之介電質陶瓷於介電質陶瓷層之厚度未達1 μm時是否仍如上述般，可靠性較高，具有良好之溫度特性且高溫負荷壽命特性優異。不如推測於介電質陶瓷層之厚度未達1 μm時，可靠性、尤其是高溫負荷壽命特性劣化之可能性較高。
[先前技術文獻] [專利文獻]
[專利文獻1]日本專利特開2005-145791號公報
因此，本發明之目之在於提供一種即便介電質陶瓷層之薄層化不斷推進，仍可實現較高之可靠性之介電質陶瓷及使用該介電質陶瓷而構成之積層陶瓷電容器。
本發明之介電質陶瓷之特徵在於，含有通式：(Ba1-x/100 Cax/100 )m TiO3 (其中，0≦x≦20)所表示之化合物作為主成分，含有aMg-bSi-cMn-dR(其中，R為選自La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu及Y中之至少1種，a、b、c及d[莫耳份]相對於上述主成分100莫耳份，分別滿足0.1<a≦20.0、0.5<b≦20.0、0.1<c≦10.0、及1.0<d≦30.0之各條件)作為副成分，且焙燒該介電質陶瓷而得之燒結體中之結晶粒子的平均粒徑為20 nm以上且未達100 nm。
又，本發明之目的亦在於一種積層陶瓷電容器，其包含：電容器本體，其係包含經積層之複數個介電質陶瓷層、及沿著介電質陶瓷層間之特定界面所形成之複數個內部電極而構成；以及複數個外部電極，其形成於電容器本體之外表面上之彼此不同之位置且電氣連接於內部電極之特定者。
本發明之積層陶瓷電容器之特徵在於，介電質陶瓷層之厚度未達1 μm，且該介電質陶瓷層包含上述本發明之介電質陶瓷之燒結體。
根據本發明之介電質陶瓷，藉由一面具有如上所述之組成，一面如上述般選擇其燒結體中之結晶粒子之平均粒徑，可形成絕緣性較強之晶界，並且可使該晶界均勻且具有一定面積地分散於燒結體中。
因此，若以本發明之介電質陶瓷構成積層陶瓷電容器，即便將介電質陶瓷層之厚度薄層化至未達1 μm，亦可獲得可靠性、尤其是壽命特性優異之積層陶瓷電容器。
本發明係關於具有如上所述之組成之介電質陶瓷，發現其結晶粒子之平均粒徑低於100 nm時，可顯著表現出如上所述之壽命特性提高效果，此點尤具重大意義。
參照圖1，首先，對應用本發明之介電質陶瓷之積層陶瓷電容器1進行說明。
積層陶瓷電容器1包含電容器本體5，其係包含經積層之複數個介電質陶瓷層2、與沿著介電質陶瓷層2間之特定界面形成之複數個內部電極3及4而構成。內部電極3及4例如以Ni作為主成分。
於電容器本體5之外表面上彼此不同之位置形成有第1及第2外部電極6及7。外部電極6及7例如以Ag或Cu作為主成分。圖1所示積層陶瓷電容器1中，第1及第2外部電極6及7形成於電容器本體5之相互對向之各端面上。內部電極3及4包括電氣連接於第1外部電極6之複數個第1內部電極3、與電氣連接於第2外部電極7之複數個第2內部電極4，於積層方向觀之，該等第1及第2內部電極3及4為交互配置。
再者，積層陶瓷電容器1可為包含2個外部電極6及7之二端子型者，亦可為包含多個外部電極之多端子型者。
於上述積層陶瓷電容器1中，位於相互對向之內部電極3及4間之介電質陶瓷層2之厚度未達1 μm。
又，介電質陶瓷層2係由含有通式：(Ba1-x/100 Cax/100 )m TiO3 (其中，0≦x≦20)所表示之化合物作為主成分，且含有aMg-bSi-cMn-dR(其中，R為選自La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu及Y中之至少1種，a、b、c及d[莫耳份]相對於上述主成分100莫耳份，分別滿足0.1<a≦20.0、0.5<b≦20.0、0.1<c≦10.0、及1.0<d≦30.0之各條件)作為副成分之介電質陶瓷之燒結體所構成。並且，該介電質陶瓷之燒結體中之結晶粒子之平均粒徑為20 nm以上且未達100 nm。
再者，適當設定(Ba,Ca)/Ti比m，較佳為於0.99~1.04之範圍內選擇。
於製作用於介電質陶瓷之原料時，首先，製作作為主成分之(Ba1-x/100 Cax/100 )m TiO3 粉末。因此，使用以特定之比例混合分別含有主成分之構成元素即Ba、Ca及Ti之氧化物、碳酸物、氯化物、金屬有機化合物等化合物粉末並進行預燒之固相合成法。再者，亦可使用水熱合成法、水解法等替代上述固相合成法。使主成分粉末形成為平均粒徑10 nm左右之微粒。
另一方面，準備作為副成分之含有R、Si、Mn及R(其中，R為選自La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu及Y中之至少1種)之各元素之氧化物、碳酸物、氯化物、金屬有機化合物等化合物粉末。並且，將該等副成分粉末以特定之比例與上述主成分粉末加以混合，由此形成用於介電質陶瓷之原料粉末。
為製造積層陶瓷電容器1，實施以下步驟：使用以上述方式獲得之介電質陶瓷原料粉末而製作陶瓷漿料，由該陶瓷漿料形成陶瓷生片，積層該等複數片陶瓷生片，藉此獲得應成為電容器本體5之未經加工之積層體，並焙燒該未經加工之積層體。於焙燒該未經加工之積層體之步驟中，焙燒如上述般所調配之介電質陶瓷原料粉末，獲得包含經燒結之介電質陶瓷之介電質陶瓷層2。
以下，對基於本發明而實施之實驗例進行說明。
[實驗例1]
(A)　介電質陶瓷原料之製作
準備微粒之BaCO3 、CaCO3 及TiO2 之各粉末作為起始原料。繼而，將該等粉末以成為主成分即(Ba1-x/100 Cax/100 )1.01 TiO3 之組成之方式稱量後，利用球磨機加以混合。此處，關於Ca量x，如表1之「Ca量x」欄中所示。
繼而，藉由預燒合成上述混合粉末，獲得(Ba1-x/100 Cax/100 )1.01 TiO3 主成分粉末。獲得之主成分粉末之平均粒徑為10 nm左右。又，根據XRD(X-ray diffraction，X射線繞射)，主成分粉末中之未反應物低於檢測水平。即，可確認主成分粉末雖為非常小之微粒，但仍為合成度較高之粉末。
另一方面，準備作為副成分之MgO、MnCO3 、SiO2 、及R2 O3 之各粉末。再者，作為R2 O3 粉末，準備La2 O3 、Ce2 O3 、Pr2 O3 、Nd2 O3 、Sm2 O3 、Eu2 O3 、Gd2 O3 、Tb2 O3 、Dy2 O3 、Ho2 O3 、Er2 O3 、Tm2 O3 、Yb2 O3 、Lu2 O3 及Y2 O3 之各粉末。
繼而，關於R2 O3 粉末，一面如表1之「R成分明細」欄所示般進行選擇，一面相對於上述主成分100莫耳份，以表1之「Mg量a」、「Si量b」、「Mn量c」及「R量d」所示之莫耳比調配上述副成分即MgO、MnCO3 、SiO2 、及R2 O3 之各粉末，將水作為介質，利用球磨機混合10小時。然後，藉由蒸發乾燥而獲得介電質陶瓷原料粉末。
(B)　積層陶瓷電容器之製作
於上述陶瓷原料粉末中添加聚乙烯丁醛系黏合劑及乙醇，利用球磨機濕式混合24小時後，進行過濾，藉此製作將具有特定範圍內之粒徑以外之粒徑的粉末排除在外之陶瓷漿料。
繼而，利用邊緣(lip)方式使該陶瓷漿料成形為片狀，獲得陶瓷生片。如下所述，陶瓷生片之厚度於焙燒後如表2之「陶瓷層厚」之欄所示。
其次，於上述陶瓷生片上網版印刷以Ni作為主體之導電膏，形成應成為內部電極之導電膏膜。
接著，將形成有導電膏膜之陶瓷生片以導電膏膜之抽出側彼此不同之方式積層複數片，獲得應成為電容器本體之未經加工之積層體。
繼而，將未經加工之積層體於N2 環境中加熱至300℃之溫度，使黏合劑燃燒後，以50℃/min之速度升溫，於氧分壓為10-10 Mpa之包含H2 -N2 -H2 O氣體之還原性環境中，在1200℃之溫度下焙燒5小時，獲得經燒結之電容器本體。
接著，於焙燒後之電容器本體之兩端面塗佈含有B2 O3 -Li2 O-SiO2 -BaO系玻璃料之Cu膏，在N2 環境中以800℃之溫度進行燒結，形成與內部電極電氣連接之外部電極，獲得成為試樣之積層陶瓷電容器。
以上述方式獲得之積層陶瓷電容器之外形尺寸為長度0.9 mm、寬度1.8 mm、厚度1.0 mm，有效介電質陶瓷層之層數為100層，每層陶瓷層之內部電極之對向面積為1.8 mm2 。介於內部電極間之介電質陶瓷層之厚度如表2之「陶瓷層厚」所示。
(C)　陶瓷結構分析及特性評價
[平均粒徑]
使各試樣之積層陶瓷電容器斷裂，於1000℃之溫度下進行熱蝕刻(thermal etching)，使用掃描式顯微鏡觀察斷裂面。並且，對所得之觀察影像中出現之結晶粒子進行圖像分析，以結晶粒子之圓當量直徑(equivalent circular diameter)作為粒徑，測定結晶粒子之粒徑。此處，對於各試樣，測定300個結晶粒子之粒徑，求出其平均值。
[高溫負荷壽命試驗]
實施高溫負荷壽命試驗，其於溫度105℃下，對各試樣之積層陶瓷電容器施加DC電壓以成為6.3 kV/mm及12.6 kV/mm之各電場強度。此處，針對各試樣，對100個試樣實施高溫負荷壽命試驗，將經過1000小時之前絕緣電阻值變成100 kΩ以下之試樣判定為不良，求出試樣數100個中之不良個數。
以上結果示於表2中。
表1及表2中，於試樣編號上附有*者為本發明之範圍外之試樣。
(D)　考察
試樣1~25之任一者之陶瓷層厚均為1 μm以下。
根據處於本發明之範圍內之試樣1~5及7~14，平均粒徑為20 nm以上且未達100 nm，表現出良好之可靠性。尤其是試樣2~5及8~12及14，不僅於電場強度6.3 kV/mm下，而且即便於電場強度12.6 kV/mm下，高溫負荷壽命試驗中之不良個數亦為0，表現出較高之可靠性。推測其原因在於，由於試樣2~5及8~12及14之主成分為(Ba,Ca)TiO3 ，故而即便結晶粒子微小，亦可製作出絕緣性優異之結晶粒子。
相對於此，試樣6之可靠性較低。推測其原因在於，Ca量x超過20莫耳，難以藉由焙燒而變得細密，機械強度較差。
試樣15~17之可靠性亦較低。推測其原因在於，平均粒徑為100 nm以上。
試樣18之可靠性亦較低。推測其原因在於，Mg量a超過20.0莫耳，而產生偏析。試樣24之可靠性亦較低。推測其原因在於，R量d超過30.0莫耳，而產生偏析。
試樣19之可靠性亦較低。推測其原因在於，Mg量a未達0.1莫耳，無法抑制晶粒生長。試樣25之可靠性亦較低。推測其原因在於，R量d未達1.0莫耳，無法抑制晶粒生長。
試樣20之可靠性亦較低。推測其原因在於，Si量b超過20.0莫耳，而產生偏析。試樣21之可靠性亦較低。推測其原因在於，Si量b為0.5莫耳以下，無法與Ba製備充分之液相，難以細密化。
試樣22之可靠性亦較低。推測其原因在於，Mn量c超過10.0莫耳，釋出電子，初始IR(Insulation Resistance，絕緣電阻)下降。試樣23之可靠性亦較低。推測其原因在於，Mn量c為0.1莫耳以下，燒結性惡化，機械強度下降。
[實驗例2]
於實驗例2中評價雜質之影響。
於原料製作等積層陶瓷電容器之製造過程中，Sr、Zr、Hf、Zn、Na、Ag、Pd及Ni等有可能以雜質之形式混入介電質陶瓷中，該等有可能存在於結晶粒子內及佔據結晶粒子間之晶界中。又，於積層陶瓷電容器之焙燒步驟等中，內部電極成分有可能擴散並存在於介電質陶瓷中之結晶粒子內及佔據結晶粒子間之晶界中。實驗例2係欲評價該等雜質之影響者。
(A)　介電質陶瓷原料之製作
於組成式：100(Ba0.95 Ca0.05 )TiO3 +2.0MgO+1.8SiO2 +1.0MnO+8.0DyO3 /2 所表示之組成中添加表3所示之雜質成分，除此以外，經由與實驗例1之情形相同之操作，獲得介電質陶瓷原料。
(B)　積層陶瓷電容器之製作
使用上述介電質陶瓷原料，以與實驗例1之情形相同之方式製作各試樣之積層陶瓷電容器。介於內部電極間之介電質陶瓷層之厚度如表4之「陶瓷層厚」所示。
(C)陶瓷結構分析及特性評價
以與實驗例1之情形相同之方式進行陶瓷結構分析及特性評價。將其結果示於表4中。
(D)　考察
由表4可知，於混入雜質之試樣101~110之任一者中，陶瓷層厚為1 μm以下，平均粒徑為20 nm以上且未達100 nm，於電場強度為6.3 kV/mm及12.6 kV/mm下，高溫負荷壽命試驗中之不良個數均為0，表現出較高之可靠性。
1．．．積層陶瓷電容器
2．．．介電質陶瓷層
3、4．．．內部電極
5．．．電容器本體
6、7．．．外部電極
圖1係圖解表示使用本發明之介電質陶瓷所構成之積層陶瓷電容器1之剖面圖。
1．．．積層陶瓷電容器
2．．．介電質陶瓷層
3、4．．．內部電極
5．．．電容器本體
6、7．．．外部電極

Claims (2)

  1. 一種介電質陶瓷，其特徵在於，包含通式：(Ba1-x/100 Cax/100 )m TiO3 (其中，0≦x≦20)所示化合物作為主成分，並包含aMg-bSi-cMn-dR(其中，R為選自La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Dy及Ho中之至少1種，a、b、c及d[莫耳份]相對於上述主成分100莫耳份，分別滿足0.1<a≦20.0、0.5<b≦20.0、0.1<c≦10.0及1.0<d≦30.0之各條件)作為副成分，且焙燒該介電質陶瓷所得燒結體中之結晶粒子的平均粒徑為20nm以上且未達100nm。
  2. 一種積層陶瓷電容器，其包含：電容器本體，其係包含經積層之複數個介電質陶瓷層、及沿著上述介電質陶瓷層間之特定界面形成之複數個內部電極而構成，以及複數個外部電極，形成於上述電容器本體之外表面上彼此不同之位置，且電氣連接於上述內部電極之特定者；並且上述介電質陶瓷層之厚度未達1μm，且包含如請求項1之介電質陶瓷之燒結體。
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JP5514437B2 (ja) * 2007-12-28 2014-06-04 三菱マテリアル株式会社 誘電体薄膜の製造方法。
JP5093351B2 (ja) * 2008-07-29 2012-12-12 株式会社村田製作所 積層セラミックコンデンサ
JP2010040798A (ja) * 2008-08-06 2010-02-18 Murata Mfg Co Ltd 積層セラミックコンデンサ
JP5295082B2 (ja) * 2009-06-25 2013-09-18 京セラ株式会社 積層セラミックコンデンサ

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CN102190488B (zh) 2013-04-03
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US8404607B2 (en) 2013-03-26

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