TW200539203A - Dielectric ceramic composition and laminated ceramic condenser - Google Patents

Dielectric ceramic composition and laminated ceramic condenser Download PDF

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Publication number
TW200539203A
TW200539203A TW094105274A TW94105274A TW200539203A TW 200539203 A TW200539203 A TW 200539203A TW 094105274 A TW094105274 A TW 094105274A TW 94105274 A TW94105274 A TW 94105274A TW 200539203 A TW200539203 A TW 200539203A
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Taiwan
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dielectric ceramic
main component
dielectric
sample
ceramic composition
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TW094105274A
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English (en)
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TWI265536B (en
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Koichi Banno
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Murata Manufacturing Co
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Description

200539203 九、發明說明： 【發明所屬之技術領域】 本發明係關於一種介電體陶瓷組合物以及積層陶瓷電容 為，更特定言之係關於一種即使於高電壓直流下或高頻/高 電壓父流下使用φ纟有高可靠性之介電體陶瓷組合物以及 積層陶瓷電容器。 【先前技術】 • 先則較多於低頻、低電壓交流下或低電壓直流下使用 積層陶瓷電容器。但是，近年來，隨著電子裝置之發展， 電子零件之小型化得以南速發展，且推動積層陶瓷電容器 之小型化、大電容化。因此，施加於積層陶瓷電容器之一 組對向電極間的電壓傾向於相對增大，故而於如此苛刻條 件下，業者強烈要求大電容、低損耗化'絕緣性之提高、 絕緣耐性之提高以及可靠性之提高。 因此’例如於專利文獻1、專利文獻2以及專利文獻3中提 • 出有可耐咼頻、高電壓交流下或高電壓直流下之使用的介 電體陶瓷組合物以及積層陶瓷電容器。 揭示於專利文獻丨中之介電體陶瓷組合物，其係以一般式 AB〇3 + aR+bMK表示，ΑΒ〇3係表示鈦酸鋇固溶體之一般 式，R係選自 La、Ce、Pr、Nd、Sm、Ευ、Gd、Tb、Dy、 Ho、Er、Tm、Yb以及Lu之至少一種氧化物類，M係選自 Μη、Ni、Mg、Fe、A卜Cr以及Zn之至少一種氧化物類， A/B(莫耳比）、a及 b係滿足 0.950 $ A/B $ 1.050、〇.l2$a$ 〇·30、0.04gbg0.30範圍，且對於主成分loo重量份含有 99630.doc 200539203 0.8〜8.0重量份之燒結助劑作為副成分者。進而，該介電體 陶瓷組合物，其對於！莫耳之鈦酸鋇固溶體含有〇·35莫耳以 下之X(Zr、Hf)〇3(X係選自Ba、Sr、Ca之一種以上元素）， 及/或對於1莫耳之鈦酸鋇固溶體含有〇·2〇莫耳以下之D(選 自V、Nb、Ta、Mo、W、Y以及Sc之一種以上氧化物）。該 介電體陶瓷組合物，其係於燒成溫度13〇(rc以下、比介電 常數200以上且高頻、高電壓交流下損耗較小，高電場強度 • 下絕緣電阻較高，並滿足B特性及X7R特性，高溫負荷特性 良妤。 又，揭不於專利文獻2中之耐還原性介電體陶瓷，其包含 將鈦酸鋇作為主成分之固溶體與燒結助劑，於_251以上之 溫度區域中藉由X線繞射所求得之結晶軸比c/a滿足1〇〇〇$ c/a$ 1.003之條件，並且以頻率i kHz之交流、2 Vrms/mm 以下之電場強度測定之比介電常數之溫度依存性中，未滿 •25 °C時獲得峰值之最大值，上述主成分係以一般式 φ AB〇3+aR+bM表示，於一般式中，R係含有選自La、Ce、Pr、 Nd、Sm、Eu、Gd、Tb、Dy、Ho ' Er、Tm、Yb 以及 Lu之至 少一種元素之化合物，M係包含選自Mn、Ni、Mg、Fe、A卜 Cr以及Zn之至少一種元素之金屬氧化物，A/B(莫耳比卜& η&ΜΜ^ι·ο〇〇$α/β$1〇35、〇〇〇5^$〇ι2、〇〇〇5 $bS0.12之範圍，且對於主成分1〇〇重量份含有〇·2〜4·〇重 量份之燒結助劑者。進而，該介電體陶瓷組合物係對於i莫 耳之鈦酸鋇固溶體含有0·20莫耳以下之x(Zr、Hf)〇3(x係選 自Ba、Sr、Ca之一種以上元素），及/或對於i莫耳之鈦酸鋇 99630.doc 200539203 固溶體含有0.20莫耳以下之D(選自v、Nb、Ta、M。、w、γ、
Sc P A1以及Fe之一種以上氧化物）。該介電體陶瓷組合 物，其表示於高頻/高電麼施加時損耗、發熱較小，直^ 交流負荷下穩定之絕緣電阻。 揭不於專利文獻3中之介電體陶竟組合物，其係包含鈦酸 鎖、稀土類氧化物（其中，稀土元素係Y、Sm、Eu、Gd、Tb、 Dy、Ho、Er、Tm以及Yb中之至少一種）、氧化鈣、氧化矽 且不含有氧化鎂之介電體陶究組合物，將上述鈦酸鋇、稀 土類氧化物、氧化鈣以及氧化矽分別表示為BamTi〇3、 R〇m(其中，R係稀土族元素）、Ca〇以及Si〇2，以一般式 100BamTi〇3+aR〇3/2+bCa〇+cSi〇2表示時（其中係數 1〇〇、 a、b以及c係莫耳比），m、a、b以及c分別滿足〇.99〇$ 1.030、0.5^ a^30、〇·5^ b^3〇、〇5^c^3〇之關係。該介 電體陶£組合物中，因CaC^MgC)共存時可#性會降低，故 而不含有MgO。該介電體陶瓷組合物，由於其滿足靜電電 谷之溫度特性以JIS規格規定之8特性以及EIA規格規定之 X7R特性，介電損耗較小為2·5%以下，室溫下施加4 kVDC/mm時之絕緣電阻（R)與靜電電容（c)之乘積（cr)為 10000 Ω F以上，向溫高電壓下之絕緣電阻之加速壽命較 長’故而即使實行薄層化亦可構成可靠性良好的積層陶竞 電容器之介電體陶瓷層。 專利文獻1 ·日本專利特開2〇〇〇_iq3668號公報 專利文獻2:日本專利特開2〇〇2-5〇536號公報 專利文獻3 ··專利第3509710號公報 99630.doc 200539203 [發明所欲解決之問題] :而專利文獻1、2、3中提出之介電體陶瓷組合物，其 、二"^任何同頻/咼電壓交流下或高電壓直流下使用的 材料#且可*性較為優良’㉟由於下述諸多情形，因此於 ^此可刻使用條件下確保提高可靠性已成為—個緊迫的問 題7後業者更強烈要求電子零件之更小型大電容化， 兄且可預测出先刖使用之條件變得日益苛刻，並且可預測 到以前所未有的程度提高可靠性。 本發明係為解決上述問題而成者，其目的在於提供一種 介電體H组合物以及積層陶变電容器，其係即使今後實 灯更小型大電容化，亦可於高電壓直流下或高頻/高電壓交 流下使用時降低發熱，與先前相&，該比介電常數、電阻 率不會劣化，具有高可靠性者。 【發明内容】 如本發明之請求項1之介電體陶瓷組合物，其特徵在於： 含有以組成式 100BamTi〇3+xCuO+aROn+bMnO+cMg〇(其 中，係數1〇〇、X、a、b以及c分別表示莫耳比，m表示以與 Τι之比（Ba/Ti)，R表示選自 γ、La、Ce、pr、Nd、Sm、Eu、
Gd、Tb、Dy、Ho、Er、Tm、Yb以及Lu之至少一種金屬元 素，n表示R化合價決定且用於保持電性中性所需之正數） 表示之主成分，上述組成式之111、：^、&、|3以及(：分別滿足〇 99〇 1·050、0·1^χ^5·〇、9.〇^a^2〇 〇、〇 5^b^3 5以 及0<cg4.0之關係，且對於上述主成分1〇〇重量份含有 0.8〜5.0重量份之燒結助劑。 99630.doc 200539203 又，如本發明之請求項2之介電體陶瓷組合物，其係如請 求項1之發明中，作為上述主成分中之添加成分，含有 M〇(其中，Μ表示選自犯及〜之至少一種金屬元素），其組 成式為 10〇BamTi〇3+xcu〇 + aR〇n + bMn〇 + cMg〇+ dM〇時該 、、且成式之c、d分別滿足〇<c+ 4.0且〇<〇1之關係。 如本發明之請求項3之介電體陶瓷組合物，其係如請求項 1或明求項2之發明中，作為上述主成分中之添加成分，對 於1〇〇莫耳之BamTi〇3，含有大於〇且小於15莫耳範圍之 X(Zr Hf)〇3(其中，X表示選自Ba、^及Ca之至少一種金 元素）。 如本發明之請求項4之介電體陶瓷組合物，其係在如請求 項1至请求項3中任何一項之發明申，上述燒結助劑係以〇2。 如本發明之請求項5之積層陶瓷電容器，其特徵在於··具 備有積層之複數個介電體陶瓷層，配置於該等介電體陶瓷 層間之内部電#，電性連接於該等内部電極之外部電極， 上述介電體陶究層係含有如請求項1至請求項4中任何一項 之介電體陶瓷組合物。 如本發明之請求項6之積層陶究電容器，其係在如請求項 5之發明中’上述内部電極係含有將犯或其合金、或^或其 合金作為主成分之導電性材料。 、 並且，本發明《彳電體陶究組合物係含有 画㈣观条Mg0之主成分。即於= 電體陶究組合物之主成分中添加基本組合BamTi〇3、R〇 :丨 ΜπΟ以外，重新添加Cu〇以及Mg〇,藉此可抑制高電麼直 99630.doc 200539203 流下或高頻/高電壓交流下使用時之發熱，並且可獲得比介 電常數，電阻率不會劣於先前，且具有高可靠性之介電體 陶瓷組合物，從而今後可作為更小型大電容之積層陶瓷電 容器之介電體材料而使用。上述組合物中之m、X、&、b以 及C分別滿足 0.990 S ms 1.050、〇·1 g 5 〇、9 〇g 20.0、 0.5$b$3.5 以及 0<c$4.0之關係。 構成上述介電體陶究組合物之主成分的鈦酸鋇 中之Ba與Ti之比（Ba/Ti)m滿足〇 990$ ! 〇5〇。若該比爪 未滿0.990則t阻率較低未滿1〇nDm，又，若以超社〇5〇 則會縮短兩溫負荷可靠性試驗中之平均故障時間。 對於100BamTi〇3之Cu0之含有量χ之莫耳比滿足〇 5.0。 若Cu0之含有tx未滿G1，則平均故障時間較短未滿 ⑽小時且可靠性較低，χ，若χ超過5.〇則電阻率較低未滿 對於嶋amTi〇3之R〇n之含有量3之莫耳比滿足9仏各 2〇.〇。當ROn之含有量3未滿9.叫平均故障時間較短未滿⑽ J寺且可罪性杈低’又，當a超過2〇〇時比介電常數較低。 肌可包含選自 Y、La、Ce、Pr、Nd、Sm、Eu、GdTb、
Dy、Ho、Er、Tm、Yb 以及 LU夕一括從,, 亦可適當選擇兩種以上稀土族元素之氧化物， 上稀土私兀素所組合構成之複合氧仆 :。又，ROn中之n表示由稀土族^純化合價決 用於保持電性中性所需之正數。 晏 之!η0之含有之莫耳比滿足〇.5“ 田n之合有未滿〇.5或超過35時，電阻率均較 99630.doc 200539203 低未滿1011 Ω m。 對於100BamTi〇3之Mg0之含有量c之莫耳比滿足〇<c ^ 4.0。MgO具有提高比介電常數之效果，當該含有量^為〇時 平均故障時間未滿100小時，超過4.〇時比介電常數會降 低。MgO具有促進稀土族元素R固溶至陶瓷粒子内之作用， 藉由添加MgO可提高可靠性。但是，當Mg〇與Ca〇共存時， 由於CaO降低MgO對於稀土族元素尺之固溶促進作用。故 • 而，較好地為實質上本發明之介電體陶瓷組合物未含有 CaO ^但是，製造本發明之介電體陶瓷組合物時，不可避 免地混入有CaO。不可避免地混入之Ca〇含有量，其對於ι〇〇 莫耳之BamTi〇3而言較好地為未滿〇.5莫耳，更好地為未滿 0.3莫耳。此處，所謂“實質上未含有Ca〇”係指亦可少量 含有不可避免地混入之CaO。 又，本赉明之介電體陶瓷組合物，其對於上述主成分1〇〇 重量份含有0.8〜5.0重量份之燒結助劑作為副成分。當對於 φ 主成分1〇〇重量份之燒結助劑含有量未滿0.8重量份時難以 穩定燒結，又，當該含有量超過5.0重量份時，平均故障時 間未滿100小時從而降低可靠性。作為燒結助劑，因可使用 先前眾所周知者，故而對此並未加以特別限定，本發明中 較好地可使用例如Si〇2。 本發明之介電體陶瓷組合物，其含有M0作為上述主成分 中之添加成分，以 100BamTi〇3+xCuO+aR〇n+bMn〇+cMg〇 +dMO表示該組成式時，較好地為該組成式之c、心分別滿足 〇<c + d$4.0且〇<d之關係。此處，M表示選自犯以及Zn之至 99630.doc 200539203 少一種金屬元素。故而，“◦係包含該任何一種金屬氧化物 者’亦可係包含兩種金屬氧化物之複合氧化物。藉由於主 成分中添加MO ’從而具有與未添加M〇之情形相比更能提 高比介電常數之效果，當對於主成分中之1〇〇莫耳之 BamTi〇3的MO含有量超過4〇莫耳時，與未添加M〇之情形 相比反而降低比介電常數。 本發明之介電體陶瓷組合物，其較好地為作為上述主成 分中之添加成分，含有對於1〇〇莫耳之BamTi〇3為大於〇且小 於1 5莫耳範圍之x(Zr、Hf)〇3。藉由於主成分中添加x(Zr、 Hf)〇3，從而具有與未添加χ(ΖΓ、Hf)〇3之情形相比更能提 咼比介電常數以及增加平均故障時間之效果，但當對於主 成分中之100莫耳之BamTi〇3的x(Zr、Hf)〇3含有量超過15 〇 莫耳時，與未含有X(Zr、Hf)〇3之情形相比反而降低比介電 常數。此處，X表示選自Ba、Sr以及Ca之至少一種金屬元 素。又，對於X(Zr、Hf)〇3中之心與财之比率，雖然不會加 φ 以特別限定，但為獲得良好之燒結性，Hf對於心之比率較 好地為30莫耳％以下。 作為上述介電體陶瓷組合物之原料粉末之製造方法，只 要可實現用BamTi〇3表示之鈦酸鋇之方法，就不會加以特別 限定，亦可係任何一種製造方法。作為該鈦酸鋇之製造方 法，例如可使用將原材料之混合物煅燒、固向反應之乾式 合成法、水熱合成法、加水分解法或溶膠_凝膠法等濕式人 成法。 一 又，對於主成分中之BamTi〇3之作為添加成分的汉％(其 99630.doc 12 200539203 中 ’ R係選自 Y、Sm、、Gd、Tb、Dy、Ho、Er、Tm以及
Yb之至少一種金屬元素）以及Cu、Μη、Si、Mg、Ni、zn之 =氧，物，只要其可構成本發明之介電體陶瓷，就不會限 =為乳化物粉末，作為原材料亦可使用烴氧基金屬或有機 至屬等之溶液、碳氧化物，#由該等原材料獲得 任何損害。 ' …、 猎由燒成上述原料粉末，可獲得本發明之介電體陶 合物。 ’
又’本發明之積層陶究電容器，彡具備+有本發明之介 電體陶瓷組合物之介電體陶瓷層。使用本發明之介電體陶 是組合物作為介電體陶曼層，藉此可確保比介電常數為300 、之；丨電吊數，且可獲得下述積層陶瓷電容器：i kHz、 5〇 Vms/随中之介電損耗為〇5%以下，電阻率為ι〇ιι^ 以上，高溫負荷可靠性試驗⑽。c，直流電場強度机〜叫 ^之平均故障時間較長y叫時以上且可靠性較高· kHz 1.77 kVrms/mm2高頻交流施加時的介電損耗較小為 0.8%以下，發熱較少。 又丄因構成本發明之積層陶兗電容器之内部電極係於還 ”11 w下燒成’故而較好地為將Ni或其合 ::作為主成分之導電性材料。藉此，可以低成本形成: 部電極。 [發明之效果] 根據本發明之請求項1至々杳士 貝至明求項6之發明，可提供一種介 電體陶究組合物以及積層陶究電容器，其係今後即使小型 99630.doc 13 200539203 化進—步進展’亦可降低高電Μ直流下或高頻/高電 β又力L下使用時之發熱，且比介電常數、電阻率不會劣於 先則’具有高可靠性。 【實施方式】 以下，根據圖1所示之實施形態說明本發明。再者，圖i 係模式性地表示本發明之積層陶瓷電容器之一本實施形態 的剖面圖。 如圖1所示，本實施形態之積層型陶瓷電容器1含有積層 之複數層介電體陶瓷層2與積層體4,該積層體4具有分別配 置於該等介電體陶瓷層2間之複數個第一、第二内部電極 3A 3B。於積層體4之兩端面分別形成第一、第二外部電 極5A、5B ’該等第一、第二外部電極5A、5B分別電性連接 於第一、第二内部電極3 A、3B。 如圖1所示，第一内部電極3A係自介電體陶瓷層2之一端 (同圖之左端）延伸至他端（右端）之附近為止，第二内部電極 3B係自介電體陶瓷層2之右端延伸至左端之附近為止。第 一、第二内部電極3A、3B係由例如以Ni為主成分之導電性 金屬所形成。 又，如圖1所示，第一外部電極5 A係電性連接於積層體4 内之第一内部電極3 A，第二外部電極5B係電性連接於積層 體4内之第二内部電極3B。第一、第二外部電極5A、5B係 由例如以Ag為主成分之導電性金屬所形成。再者，於第—、 第二外部電極5A、5B之表面依次施加先前眾所周知之第一 電鍍層6A、6B以及第二電鍍層7A、7B。 99630.doc -14- 200539203 實施例1 其次，依據具體實施例說明本發明。本實施例中，以下 述順序調製表1所示之樣本Ν〇· 1〜49之介 電體陶瓷組合物 後，使用該等樣本以下述順序製作各個積層陶瓷電容器。 其次，分別評估該等積層陶瓷電容器之電特性，將其呼估 結果表示於表2。再者，於表！以及表2中，附有*記號之樣 本係超出本發明之範圍者。
表1以及表2所示之樣本〜49,其係用於觀察介電體陶 莞組合物之主成分⑽BamTi()3+x⑽+aRGn+bM命吨⑺ 之m、X、R(稀土族元素）、a、b、e以及燒結助劑含有量『(對 於主成分100重量份之重量份）之影響的樣本，且係將該等 各因素之任意一個自本發明之範圍轉至本發明之範圍外， 於本發明之範圍内固定其他因素所調製者。 (1)介電體陶瓷組合物之調製 首先，分別稱重表1所示之各原材料後將其混合，準備且 有表m示之組合之原料粉末。其次，於該等原料粉末^ 加聚乙烯醇縮丁醛系黏合劑以及乙醇等之有機溶劑，藉由 球磨機濕式混合，從而調製陶t衆料作為介電體陶竟：合 物。本實施例中，使用Si〇2作為燒結助劑。 (2)積層陶瓷電容器之製作 藉由刮墨刀法將(1)中獲得之陶瓷漿料成形為薄片狀，声 得厚度—之陶究生片後’於該陶究生片上藉由絲網印： 法印刷將Ni作為主成分之導電膏，從而形成用於構成内部 電極之導電膏膜。 99630.doc 200539203 "★圖1所不以導電膏膜之引出側相互 數枚積層陶瓷生μ，％&從 丨j之方式稷 # 片從而獲得未加工之陶竞積層體。於氮 k未加工之陶究積層體加熱至350t且燃燒 黏合劑後，於氧分懕盔 9 1〇 MPa且包含H2-N2-H2〇氣體 之遇原性裱境下，以表 7丁之1度燒成未加工之陶瓷積層 _ A '、時，從而獲得積層陶瓷燒結體。 另-方面，準備含有B2〇3_Si(VBa〇系玻璃粉之銀漿，將
該銀漿塗敷於積層陶兗燒結體之兩端面。繼而，於n2環境 下以600 C之溫度將銀漿燒成於積層陶瓷燒結體之兩端 於積層陶瓷燒結體之兩端面形成電性連接於第一、 第-内部電極之第―、第二外部電極後，冑電鍵處理分為 兩個階段實施於第一、第二外部電極表面形成第一、第二 電從而獲得積層陶究電容器。如此獲得之積層陶瓷 電备益之外形尺寸係寬度為3 2 _、長度為45麵、厚度 ,〇·5 mm ’介存於第一、第二内部電極間之介電體陶瓷層 厚度係iG 又，介電體陶究層之有效積層數係5,每一 層對向電極面積紅5 ⑽如此獲得之樣本㈤〜衫 之積層陶究電容器，實行如下所示之各電性特性之評估， 將其結果表示於表2。 (3)積層陶£電容器之電性特性之評估方法以及評估結果 A)比介電常數（sr)以及介電損耗（tan§) 關於樣本No·1〜49，使用自動橋接器式測定器施力。1 kHz、50 Vrms/mm之訊號電壓從而測定各靜電電容⑹以及 介電損耗（㈤），根據各靜電電容之測定值與各積層陶究電 99630.doc -16- 200539203 容器之構造分別算出比介電常數（h)，將其結果表示於表2。 B)電阻率) 關於樣本No. 1〜49，使用絕緣電阻計分別向各樣本施加 300 v之直流電壓60秒，求得25°C下之絕緣電阻值（R)，分 別异出電阻率（p)，將其結果表示於下述表3及表4。 c)平均故障時間（MTTF)
作為樣本No· 1〜49之兩溫負荷可靠性試驗，溫度17$。〇下 分別將400 V之直流電壓施加於各樣本，從而測定各絕緣電 阻之常時變化。此時，高溫負荷可靠性試驗係將各樣本之 絕緣電阻值（R)成為心以下之時刻判定為故障，分別求得 平均故障時間（MTTF)，將其結果表示於表2。 D)高頻施加時之介電損耗（tan占） 關於樣本No. 1〜49，為評估高頻交流施加 施加300 kHz、1·77 kVrms/mm之訊號電壓 損耗（tan 6 )，將其結果表示於表2。 時之發熱，故而 ’從而測定介電
99630.doc 200539203 [表l]
100.0 BamTi〇3 + xCuO + aROn+bMnO + cMgO+fSi〇2 樣本No. m X R a b c f *1 0.980 1.0 Gd 12.0 1.0 2.0 1.25 2 0.990 1.0 Gd 12.0 1.0 2.0 1.25 3 1.015 1.0 Gd 12.0 1.0 2.0 1.25 4 1.030 1.0 Gd 12.0 1.0 2.0 1.25 5 1.050 1.0 Gd 12.0 1.0 2.0 1.25 *6 1.060 1.0 Gd 12.0 1.0 2.0 1.25 氺7 1.015 0.0 Gd 9.0 1.0 2.0 1.25 8 1.015 0.1 Gd 9.0 1.0 2.0 1.25 9 1.015 0.5 Gd 9.0 1.0 2.0 1.25 10 1.015 2.0 Gd 9.0 1.0 2.0 1.25 11 1.015 5.0 Gd 9.0 1.0 2.0 1.25 *12 1.015 6.0 Gd 9.0 1.0 2.0 1.25 *13 1.015 1.0 Gd 8.0 1.0 2.0 1.25 14 1.015 1.0 Gd 9.0 1.0 2.0 1.25 15 1.015 1.0 Gd 15.0 1.0 2.0 1.25 16 L015 1.0 Gd 18.0 1.0 2.0 1.25 17 1.015 1.0 Gd 20.0 LO 2.0 1.25 *18 1.015 1.0 Gd 21.0 1.0 2.0 1.25 *19 1.015 1.0 Gd 9.0 0.0 2.0 1.25 *20 1.015 1.0 Gd 9.0 0.2 2.0 1.25 21 1.015 1.0 Gd 9.0 0.5 2.0 1.25 22 1.015 1.0 Gd 9.0 2.0 2.0 1.25 23 1.015 1.0 Gd 9.0 3.5 2.0 1.25 *24 1.015 1.0 Gd 9.0 4.0 2.0 1.25 *25 1.015 1.0 Gd 9.0 1.0 0.0 1.25 26 1.015 1.0 Gd 9.0 1.0 1.0 1.25 27 1.015 1.0 Gd 12.0 1.0 3.0 1.25 28 1.015 1.0 Gd 20.0 1.0 4.0 1.25 *29 1.015 1.0 Gd 20.0 1.0 5.0 1.25 *30 1.015 1.0 Gd 12.0 1.0 2.0 0.60 31 1.015 1.0 Gd 12.0 1.0 2.0 0.80 32 1.015 1.0 Gd 12.0 1.0 2.0 1.50 33 1.015 1.0 Gd 12.0 1.0 2.0 3.00 34 1.015 1.0 Gd 12.0 1.0 2.0 5.00 *35 1.015 1.0 Gd 12.0 1.0 2.0 6.00 36 1.015 1.0 Y 12.0 1.0 2.0 1.25 37 1.015 1.0 La 12.0 1.0 2.0 1.25 38 1.015 1.0 Ce 12.0 1.0 2.0 1.25 99630.doc -18- 200539203 [表2] 39 1.015 1.0 Pr 12.0 1.0 2.0 1.25 40 1.015 1.0 Nd 12.0 1.0 2.0 1.25 41 1.015 1.0 Sm 12.0 1.0 2.0 1.25 42 1.015 1.0 Eu 12.0 1.0 2.0 1.25 43 1.015 1.0 Tb 12.0 1.0 2.0 1.25 44 1.015 1.0 Dy 12.0 1.0 2.0 1.25 45 1.015 1.0 Ho 12.0 1.0 2.0 1.25 46 1.015 1.0 Er 12.0 1.0 2.0 1.25 47 1.015 1.0 Tm 12.0 1.0 2.0 1.25 48 1.015 1.0 Yb 12.0 1.0 2.0 1.25 49 1.015 1.0 Lu 12.0 1.0 2.0 1.25
1 OO.QBamTi〇3 + xCuO+aROn+bMnO + cMgO + fSi〇2
樣本No. 燒成溫度[°C] εΓ[-] tan[%] p [Qm] MTTF[小時] 300 kHz *1 1200 680 0.3 9.5χ101ϋ 90 1.8 2 1200 670 0.3 2.5xlOn 120 0.8 3 1200 650 0.2 7.3χ10π 140 0.6 4 1250 630 0.2 3.4χ10π 120 0.6 5 1275 620 0.4 6.2xlOu 115 0.7 *6 1300 600 0.6 5.4xlOu 90 1.8 *7 1225 670 0.3 7.2Χ1011 90 0.6 8 1225 660 0.2 8.1Χ1011 110 0.6 9 1225 650 0.2 8.3χ101ϋ 120 0.7 10 1225 650 0.3 7.5χ10π 160 0.7 11 1175 630 0.3 2·5χ10π 140 0.7 *12 1175 630 0.4 8.3χ101ϋ 110 1.2 *13 1175 900 0.3 8.0xl0u 90 0.7 14 1200 830 0.2 7.8Χ1011 110 0.7 15 1250 550 0.2 5.2Χ1011 160 0.5 16 1275 450 0.1 4.6χ10π 200 0.4 17 1300 340 0.1 6.5Χ1011 220 0.3 *18 1300 280 0.1 4·1χ10π 230 0.3 *19 1250 - - 6.5χ107 - - *20 1250 670 0.6 8.5χ101ϋ 85 1.5 21 1225 650 0.4 8.2Χ1011 135 0.7 22 1200 650 0.2 2·0χ1012 160 0.6 23 1200 630 0.2 3.3χ10π 180 0.6 *24 1200 600 0.4 9.0χ101ϋ 190 0.9 *25 1200 760 0.3 8.3Χ1011 80 0.8 26 1200 800 0.2 8.5Χ1011 105 0.7 99630.doc -19- 200539203 27 1200 650 0.3 7.5X1011 140 0.6 28 1300 320 0.1 8.4χ10π 240 0.3 *29 1300 280 0.1 7.4χ10π 250 0.2 *30 燒結不足 - 31 1250 600 0.4 2.3χ1012 135 0.8 32 1175 650 0.3 1.8χ1012 140 0.6 33 1150 620 0.2 8.5χ10π 120 0.5 34 1100 600 0.1 6·5χ10 丨1 110 0.4 *35 1100 590 0.1 7.2χ10π 90 0.3 36 1225 630 0.3 3.5Χ1011 135 0.6 37 1175 610 0.1 4.2χ10η 135 0.4 38 1175 620 0.1 5.3Χ1011 140 0.4 39 1175 620 0.2 4.8χ10π 140 0.4 40 1175 620 0.2 6.3Χ1011 150 0.4 41 1200 630 0.2 5.7Χ101】 140 0.5 42 1200 640 0.2 5.8Χ1011 140 0.5 43 1200 640 0.2 6.4xlOu 150 0.5 44 1225 660 0.2 7.2χ10π 150 0.5 45 1225 650 0.2 9.5Χ1011 140 0.5 46 1225 640 0.3 6.5Χ10】1 140 0.6 47 1225 640 0.3 7.2Χ1011 140 0.6 48 1250 630 0.3 5.5Χ1011 135 0.6 49 1250 630 0.3 4.8χ10]1 135 0.7 藉由表2所示之結果，判斷用於觀察BamTi03中之Ba與Ti 之比m( = Ba/Ti)之影響的樣本No.l至Νο·6中，本發明之範圍 (0.990 S m $ 1.05 0)内之樣本Νο·2〜Νο·5係可確保比介電常 數（sr)為3 00以上之介電常數，且獲得下述特性：1 kHz、50 Vrms/mm中之介電損耗（tan5)為0.5%以下，電阻率（p )為 10πΩιη以上，高溫負荷可靠性試驗（175°C，直流電場強度 為40 kV/mm)中之平均故障時間（MTTF)較長為100小時以 上且可靠性較高，300 kHz、1.77 kVrms/mm之高頻交流施 加時之介電損耗（tanS)較小為0.8%以下且發熱較少，即使於 高電壓直流下或高頻/高電壓交流下使用時亦具有高可靠 性。對此，亦可判斷本發明之範圍外之樣本No. 1、6中，m 99630.doc -20- 200539203 未滿0.990之樣本N。」之特性為如下：|阻率⑷為Μ —。 Ω m低於1〇丨丨Ω m，平均故障時間⑽叫為％小時短於⑽ 小時’且300 kHz中之介電損耗（tanS)較大為18%且易於發 熱。又’可判斷m超過uso之樣本n〇6之特性為如下：平 均故障時間（MTTF)為90小時短於丨〇〇小時，3〇〇他中之介 電損耗（tan5)較大為1.8%，且較易發熱。
藉由表2所示之結果，可判斷用於觀察CuO含有量x之影 響的樣本No.7〜N〇.12中本發明之範圍（〇.κχ$5·〇)内之樣 本No.8〜No.U，其滿足任何一個上述特性評估。對此，亦 可判斷本發明之範圍外之樣本版7、12中，χ未滿〇ι且未 添加CuO之樣本Νο.7 ’其平均故障時間⑽叫為9〇小時短 1〇1()Ωπι 低於 10ηΩηι 為 1.2%。 於100小時，又’ X超過5.0之樣本N〇 12之電阻率（^ )為 且300 kHz中之介電損耗（tan 5 )較大 藉由表2所示之結果，可判斷用於觀察尺化含有量&之影響 的樣本Ν〇·13〜Ν〇·18中，本發明之範圍（9〇ga^2〇〇)内之 樣本No.14〜No.17係滿足任何_個上述特性評估。對此，亦 可判斷本發明之範圍外之樣本版13、18中，a未滿9〇之樣 本Νο·13之平均故障時間㈧丁^)為9〇小時短於ι〇〇小時， 又，a超過20.0之樣本No.18之比介電常數為28〇低於3〇〇。 藉由表2所示之結果，可判斷用於觀察]^11〇含有量b之影 響的樣本Νο·19〜Ν〇·24中，本發明之範圍（0KW3.5)内之 樣本No.21〜Νο·23係滿足任何—個上述特性評估。對此，亦 可判斷本發明之範圍外之樣本No.19、20以及24中，未含有 99630.doc •21 - 200539203
MnO之樣本Νο·19係除電阻率（p )以外無法測定其他特性，匕 未滿0·5之樣本Νο·20之電阻率（p )為85><1〇1〇〇 m低於i〇】】 Ωιη，平均故障時間（MTTF)為85小時短於1〇〇小時，又，匕 超過3·5之樣本Νο·24之電阻率（p )為9〇χ1〇1〇Ω m低於ι〇" Ω m 〇 藉由表2所示之結果，可判斷用於觀察馗11〇含有量c之影 響的樣本Νο·25〜No.29中，本發明之範圍4 〇)内之樣 本N〇·26〜ν〇·28係滿足任何一個上述特性評估。對此，亦可 判斷本發明之範圍外之樣本Ν〇·25、29中，未含有Μη〇之樣 本Νο·25之平均故障時間⑽丁丁”為8〇小時少於ι〇〇小時， 又，c超過4.0之樣本Νο·29之比介電常數⑹為28〇低於3〇〇。 藉由表2所示之結果，可判斷用於觀察燒結助劑（Si〇2)之 添加量f之影響的樣本No.30〜No.35中，本發明之範圍（〇.8 $^5.0)内之樣本]^〇.30〜>1〇.34係滿足任何一個上述特性 評估。對此’亦可判斷本發明之範圍外之樣本ν〇·30、35中， φ 添加量未滿0.8重量份之樣本N〇.3〇係不會燒結，又，添加 里超過5.0之樣本1^〇 35之平均故障時間（…丁丁^為9〇小時短 於100小時。 藉由表2所示之結果，可判斷用於觀察R〇n即稀土族元素 之氧化物種類之影響的樣本Ν〇·36〜νο·49中，只要R〇n含有 i a屬於本發明之範圍（9 〇 $ & $ 2〇.〇)内，就可滿足任何一個 上述特性評估。 ^ 實施例2 本貫知例中’如表3所示於實施例1之樣本No· 1 7之主成分 99630.doc -22- 200539203 中添加Ni〇或ZnO作為MO，將各含有量d自本發明之較好範 圍（〇<c + d$ 4.0且0<d)轉至其範圍外，從而以與實施例1相同 順序調製樣本Νο·50〜Νο·55之介電體陶瓷組合物。其後，使 用該等樣本，以與實施例1相同順序製作積層陶瓷電容器， 與實施例1相同方式測定該等積層陶瓷電容器之電性特 性’將其測定結果表示於表4。再者，於表3以及表4中，附 有*記號之樣本係超出本發明之較好範圍外者。 [表3] l〇O.OBamTi〇3+xCuO+aROn+bMnO+cMgO+dMO+fSiO? 樣本No· m X R a b c M d c+d f 17 1.015 1.0 Gd 20.0 1.0 2.0 - 0.0 2.0 1.25 50 1.015 1.0 Gd 20.0 1.0 2.0 Ni 1.0 3.0 1.25 51 1.015 1.0 Gd 20.0 1.0 2.0 Ni 2.0 4.0 1.25 *52 1.015 1.0 Gd 20.0 1.0 2.0 Ni 3.0 5.0 1.25 53 1.015 1.0 Gd 20.0 1.0 2.0 Zn 1.0 3.0 1.25 54 1.015 1.0 Gd 20.0 1.0 2.0 Zn 2.0 4.0 1.25 *55 1.015 1.0 Gd 20.0 1.0 2.0 Zn 3.0 5.0 1.25 [表4] 1 OO.OBamTi〇3+xCuO+aR〇n + bMnO+cMgQ+dMO + fS〇9 樣本No. 燒成溫度[°C] SrH tan5[%] p [Qm] MTTF[小時] 300 kHz 17 1300 340 0.1 6.5xl010 220 0.3 50 1300 340 0.1 7.5xlOu 230 0.3 51 1300 320 0.1 8.0xl0n 230 0.3 *52 1300 280 0.1 7.3xlOu 240 0.2 53 1300 340 0.1 7.4xlOu 230 0.3 54 1300 320 0.1 7.9xlOu 240 0.3 *55 1300 280 0.1 7.0x10 丨1 240 0.2 藉由表4所示之結果，可判斷於本發明之較好範圍（〇<c+d $4.0且0<(1)内之主成分中添加川0之樣本_.5〇、51，其與 未添加NiO之樣本No.17相比，電阻率（p)較高，平均故障 時間（MTTF)較長且可靠性更高。可判斷Ni〇含有量超過本 99630.doc -23- 200539203 發明之較好範圍之樣本Ν〇·52,其比介電常數⑹雖略低於 未添加NiO之樣本^^0.17，但與樣本Ν〇17相比，電阻率（^ ) 較高且平均故障時間（MTTF)較長。可確認取代Ni〇添加a。 作為MO之樣本Νο.53〜Ν〇·55’其與添加Ni〇之情形具有相同 傾向。 實施例3 本實施例中，如表5所示於實施例1之樣本N〇172主成分 中添加Ba(Zr、Hf)03作為X(Zr、Hf)03，將其含有量e自本發 明之較好範圍（對於1〇〇莫耳之BamTi〇3，〇莫耳<e$ 15莫耳） 轉至其範圍外，從而以與實施例丨相同順序調製樣本 Νο·56〜60之介電體陶瓷組合物。其後，使用該等樣本，以 與實施例1相同順序製作積層陶瓷電容器，以與實施例1相 同方式測定該等積層陶瓷電容器之電性特性，且將其測定 結果表示於表6。再者，於表5以及表6中，附有*記號之樣 本係超出本發明之較好範圍者。 又’如表5所示於貫施例2之樣本Νο·50中添加Sr(Zr、Hf)〇3 作為X(Zr、Hf)〇3，將其含有量自本發明之較好範圍（〇<eg 15)轉至其範圍外，從而製作樣本νο·61、62之介電體陶究 組合物。並且，測定各樣本之電性特性，將其測定結果與 樣本No.50相互比較後表示於表6。又，如表5所示於實施例 2之樣本Νο·53中添加Ca(Zr、Hf)〇3作為X(Zr、Hf)03，將其 含有量自本發明之較好範圍（0<e^15)轉至其範圍外，從而 製作No.63、64之介電體陶瓷組合物。並且，測定各樣本之 電性特性，將該測定結果與樣本Νο·53相互比較後表示於表 99630.doc -24- 200539203 [表5] 100.0BamTiO3+xCuO + aROn + bMnO + cMgO+dMO+eX(Zr、
Hf)〇3 + fSi〇2 樣本No· m X R a b c M d c+d X e f 17 1.015 1.0 Gd 20.0 1.0 2.0 - 0.0 2.0 Ba 0.0 1.25 56 1.015 1.0 Gd 20.0 1.0 2.0 - 0.0 2.0 Ba 6.0 1.25 57 1.015 1.0 Gd 20.0 1.0 2.0 - 0.0 2.0 Ba 9.0 1.25 58 1.015 1.0 Gd 20.0 1.0 2.0 - 0.0 2.0 Ba 12.0 1.25 59 1.015 1·0 Gd 20.0 1.0 2.0 - 0.0 2.0 Ba 15.0 1.25 *60 1.015 1.0 Gd 20.0 1.0 2.0 - 0·0 2.0 Ba 18.0 1.25 50 1.015 1.0 Gd 20.0 1.0 2.0 Ni 1.0 3.0 Sr 0.0 1.25 61 1.015 1.0 Gd 20.0 1.0 1.0 Ni 1.0 2.0 Sr 12.0 1.25 *62 1.015 1.0 Gd 20.0 1.0 1.0 Ni 1.0 2.0 Sr 18.0 1.25 53 1.015 1.0 Gd 20.0 1.0 2.0 Zn 1.0 3.0 Ca 0.0 1.25 63 1.015 1.0 Gd 20.0 1.0 1.0 Zn 1.0 2.0 Ca 12.0 1.25 *64 1.015 1.0 Gd 20.0 1.0 1.0 Zn 1.0 2.0 Ca 18.0 1.25
[表6] 100.0BamTiO3+xCuO + aROn+bMnO + cMgO + dMO + eX(Zr >
Hf)03 + fSi0, 樣本No· 燒成溫度[°c] Brl·] -----. tan5[%l p [Ωηι] MTTF[小時] 300 kHz 17 1300 340 0.1 6·5χ1010 220 0.3 56 1300 360 0.2 6.5χ10η 230 0.3 57 1300 350 0.2 7.0χ10η 240 0.3 58 1300 330 0.1 7.5χ10η 245 0.2 59 1300 310 0.1 7.8xlOu 250 0.2 *60 1325 290 --—-------- 0.1 8.2Χ1011 260 0.2 ~~ 50 1300 340 o7\~~ 7.5χ1〇η 230 0.3 61 1200 320 ---—-- 0.1 7.5χ1〇10 240 03~ *62 __1200 280 ----- 0.1 ^Λχ\0η 250 0.2 53 _mo 340 ---- 0.1 7.4x1ο11 230 0.3 ~~ --------- 0.3 63 1200 330 0.1 λδίιο11 ο γ\^ ι 11 240 *64 — 1200 290 --—.— 0 1 V. 1 』·0χ10 250 0.2 藉由表6所不之結果，可判斷未添加m〇而是於本發明之 I乂好祀圍（〇<e ^ i 5)内之主成分中添加叫△、h⑽之樣本 99630.doc -25- 200539203 Ν〇·56〜Ν〇·59 ’其與未添加Ba(Zr、Hf)03之樣本No· 17相比， 平均故障時間（MTTF)較長且可靠性更高。可判斷Ba(Zr、 Hf)〇3含有量超過本發明之較好範圍之樣本^〜⑼，雖然其 比介電常數（ε〇略低於未添加Ba(Zr、Hf)03之樣本No.17， 但與樣本No·17相比平均故障時間（MTTF)較長且可靠性更 高。 藉由表6所示之結果，可判斷於實施例2之樣本Νο·5〇中於 本發明之較好範圍（0<e $ 15)内添加Sr(Zr、Hf)〇3之樣本 No.61，其平均故障時間（MTTF)更長。樣本ν〇·62，特別是 超過本發明之較好範圍添加Sr(Zi·、Hf)03之樣本Νο.62，雖 然其比介電常數（Sr)略低於實施例2之樣本Νο·50，但與樣本 Νο·50相比平均故障時間較長且可靠性更高。又，亦 可確為於貫施例2之樣本Νο·53中添加Ca(Zr、Hf)〇3之樣本 Νο·63、64，其具有與樣本ν〇·61、62相同之傾向。 再者，本發明係不會限制於上述實施例，只要滿足本發 明之條件，即任何態樣之介電體陶瓷組合物或積層陶究電 容器均包含於本發明中。 [產業上之可利用性] 本發明係可較好地應用於高電壓直流下或高頻/高電壓 交流下使用之積層陶瓷電容器。 【圖式簡單說明】 圖1係表示本發明之積層陶瓷電容器之一實施形態的剖 面圖。 【主要元件符號說明】 99630.doc -26- 200539203 1 積層陶瓷電容器 2 介電體陶瓷層 3A、3B 第一、第二内部電極 4 積層體 4A、4B 第一、第二外部電極 5A、5B 第一、第二外部電極
99630.doc 27-

Claims (1)

  1. 200539203 十、申請專利範圍： 1 · 一種介電體陶瓷組合物，其特徵在於··含有以組成式 100BamTi〇3+xCuO+aR〇n+bMnO+cMg〇(其中，係數 100、 x、a、b及c分別表示莫耳比，m表示Ba與Ti之比（Ba/Ti)， R表示選自 γ、La、Ce、pr、Nd、Sm、Eu、Gd、Tb、Dy、 Ho、Er、Tm、Yb及Lu中之至少一種金屬元素，n表示為 保持取決於R之價數之電中性所需之正數）表示之主成 分’上述組成式之m、X、a、b及c分別滿足以下之關係： # 0.990^ 1.050、 o.l ^ 5.0 > 9.0$ 20·0、 0.5$ 3.5及 〇<c$ 4.0，且對於上述主成分loo重量份含有〇 · 8〜5 ·〇重 量份之燒結助劑。 2·如請求項1之介電體陶瓷組合物，其中作為上述主成分中 之添加成分，含有ΜΟ(其中，Μ表示選自Ni及Ζη中之至少 ® 一種金屬元素），其組成式以l〇〇BamTi〇3+xCuO+aROn+ bMnO+cMgO+dMO表示時，該組成式之^、d分別滿足以 下之關係： 〇<c + d $ 4.0且 〇<d 〇 3 ·如請求項1或2之介電體陶竞組合物，其中作為上述主成 分中之添加成分’對於BamTi〇31〇〇莫耳在大於〇且I〗莫耳 以下之範圍含有X(Zr、Hf)〇3(其中，又表示選自Ba、^及 99630.doc 200539203 Ca中之至少一種金屬元素）。 4. 如凊求項1至3中任何一項之介電體陶瓷組合物，其中上 述燒結助劑係Si〇2。 5. :種積層陶究電容器，其特徵在於：含有積層之複數個 "電體陶究層、配置於該等介電體陶竞層間之内部電極 電f生連接於該等内部電極之外部電㉟，上 瓷層係由如& .书TS , s丄 ；丨电體陶 所形成。 中任何-項之介電體陶瓷組合物 6·如請求項5之積層陶兗電容器，其中上 :或其合金、或Cu或其合金為 糸由以 成。 等電性材料所形
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