TWI634092B - 與鎳電極倂用之ｃｏｇ介電組成物及形成電子組件之方法 - Google Patents

與鎳電極倂用之ｃｏｇ介電組成物及形成電子組件之方法 Download PDF

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TWI634092B
TWI634092B TW105119415A TW105119415A TWI634092B TW I634092 B TWI634092 B TW I634092B TW 105119415 A TW105119415 A TW 105119415A TW 105119415 A TW105119415 A TW 105119415A TW I634092 B TWI634092 B TW I634092B
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weight percent
dielectric
weight
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TW201722883A (zh
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小華特Ｊ 西墨斯
穆罕默德Ｈ 梅格希
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菲洛公司
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Abstract

依照本發明製造滿足COG要求且與還原大氣燒結條件相容，使得可將非貴金屬(如鎳與鎳合金)用於內部及外部電極之多層陶瓷片電容器。該電容器呈現所欲的介電性質(高電容、低損耗因數、高絕緣電阻)、優良的高加速壽命測試性能、及非常良好的介電崩潰抗性。該介電層包含以各種組合摻雜其他金屬氧化物(如TiO2、CaO、B2O3、與MgO)之鋯酸鋇鍶基質。

Description

與鎳電極併用之COG介電組成物及形成電子組件之方法
本發明關於基於鋯酸鹽鈦酸鹽之介電組成物，更特定而言，關於基於受摻雜鋯酸鋇鍶之介電組成物，其可用以形成具有由鎳或鎳合金形成的內部卑金屬電極之多層陶瓷片電容器。
多層陶瓷片電容器已被廣泛用作為小型高電容及高可信度電子組件。隨著高性能電子設備之需求增加，多層陶瓷片電容器亦已遭遇到更小型化、電容更高、成本更低、及可信度更高之市場要求。
多層陶瓷片電容器通常藉由形成內部電極形成糊與介電層形成糊之交錯層而製造。此層一般藉片化、印刷、或類似技術，繼而並行燒製而形成。
通常內部電極係由如鈀、金、銀、或以上的合金之導體所形成。雖然鈀、金、與銀昂貴，但其可部分使用相對不昂貴的卑金屬(如鎳及其合金)取代。「卑金屬」為金、銀、鈀、與鉑以外的任何金屬。如果在周圍空氣中燒製，則卑金屬內部電極會被氧化，故介電層與內部電極層必須在還原大氣中共燒。然而，在還原大 氣中燒製造成介電層被還原而降低電阻率。現已提議使用不還原介電材料之多層陶瓷片電容器，然而，此裝置一般為絕緣電阻(IR)壽命較短且可信度低。
電子工業協會(EIA)規定電容溫度係數(TCC)之標準，已知為COG特徵。COG特徵要求在-55℃至+125℃之溫度範圍，每度攝氏之電溶變化不超過30ppm(±30ppm/℃)。COG組件不呈現電容老化。
本發明提供一種可用以製造與含有卑金屬(如鎳或鎳合金)之內部電極相容的陶瓷多層電容器之介電組成物。該電容器可由本發明之介電組成物形成，而呈現安定的介電常數且介電損失小，及在高加速壽命測試條件下可信度優良。
本發明之介電組成物包含其顆粒之平均直徑為約0.5至約3微米之均勻稠密微結構。均勻且稠密的顆粒微結構對於獲得介電層比5微米薄之高可信度多層電容器為重要的。
在一具體實施例中，可為糊形式的本發明介電組成物在燒製前包含鋇、鍶、與鋯之氧化物的摻合物。其可加入如CaO與TiO2之氧化物以調整TCC值。因此，本發明之一具體實施例為一種包含先質(其在燒製時形成包含摻雜少量鈣與鈦之鋯酸鋇鍶基質之介電材料)的混合物之組成物。少量表示3重量百分比或以下。其可添加氧化物(如MgO與B2O3)幫助燒結。
本發明之組成物包含先質的混合物，其在燒製時形成包含摻雜少量鈣與鈦之鋯酸鋇鍶基質之介電材料。
本發明之組成物包含先質的混合物，其在燒製時形成包含：約26.5重量百分比至約34.0重量百分比之BaO；約18.0重量百分比至約24.5重量百分比之SrO；約41.0重量百分比至約50.0重量百分比之ZrO2；約0.50重量百分比至約1.50重量百分比之CaO；及約0.70重量百分比至約2.50重量百分比TiO2之介電材料。在此具體實施例中，該介電材料可進一步包含先質，使得在燒製時該介電材料進一步包含約0.10重量百分比至約1.0重量百分比之B2O3；及約0.31重量百分比至約1.47重量百分比之MgO。
本發明之一具體實施例為一種形成電子組件之方法，其包含：對基板塗佈在此他處所揭示的任何介電糊、介電材料、或任何先質混合物；及在足以燒結該介電糊、介電材料、或任何先質混合物之溫度下燒製該基板。
本發明之一具體實施例為一種多層陶瓷片電容器，其包含交錯堆疊之燒製集合體：在此他處所揭示的任何介電糊、介電材料、或任何先質混合物之層；及包含Ag、Au、Pd、或Pt以外的過渡金屬之內部電極材料之層。
本發明之一具體實施例為一種形成電子組件之方法，其包含 在基板上交錯塗佈以下之層：在此他處所揭示的任何介電糊、介電材料、或任何先質混合物，及含金屬電極糊，而形成積層堆疊；將該積層堆疊切割成預定形狀；將該切割堆疊從基板分離；及燒製該堆疊而將該電極糊中的金屬稠化，及燒結該介電糊，其中內部電極層及介電層各具有一層厚。
該方法可進一步包含將含有導電性金屬之糊塗佈於介電層與電極層之末端，及燒製形成多層電容器。該導電性金屬較佳為銅。
本發明之一具體實施例為一種包含固體部分之無鉛無鎘介電糊，其中該固體部分包含：約34.1重量百分比至約43.8重量百分比之BaCO3；約25.6重量百分比至約34.9重量百分比之SrCO3；約41.0重量百分比至約50.0重量百分比之ZrO2；約0.70重量百分比至約2.50重量百分比之TiO2；及約0.89重量百分比至約2.70重量百分比之CaCO3。
本發明之一具體實施例為一種包含固體部分之無鉛無鎘介電糊，其中該固體部分包含：約47.8重量百分比至約61.3重量百分比之BaZrO3；約1.6重量百分比至約5.7重量百分比之SrTiO3；約39.4重量百分比至約53.6重量百分比之SrZrO3； 約1.2重量百分比至約3.6重量百分比之CaTiO3；及約1.6重量百分比至約4.8重量百分比之CaZrO3。
本發明之一具體實施例為一種包含固體部分之無鉛無鎘介電糊，其中該固體部分包含：約47.8重量百分比至約61.3重量百分比之BaZrO3；約39.4重量百分比至約53.6重量百分比之SrZrO3；約1.2重量百分比至約3.6重量百分比之CaTiO3；約0.1重量百分比至約2.14重量百分比之Mg(OH)2；及約0.1重量百分比至約1.78重量百分比之H3BO3。
本發明之另一具體實施例為一種包含多層片之電子裝置，該片包含具有摻雜鈦酸鈣混合體與氧化鎂-氧化硼混合體之鋯酸鋇鍶基質之介電層。
在另一具體實施例中，本發明提供一種形成電子組件之方法，其包含將介電材料粒子施加於基板，及在足以燒結該介電材料之溫度燒製該基板，其中該介電材料在燒製前包含表1中成分的摻合物(重量比例)。亦應了解，在此各數值(百分比、溫度等)前置「約」以推定。
另一途徑係以碳酸鋇、碳酸鍶、氧化鋯、二氧化鈦、與碳酸鈣開始。關於此點，表2之調配物將生成與表1之調配物所製造者大致相同的介電材料。
該組成物亦可藉由燒製一種或以上的事先反應氧化物(如鈦酸鋇(BaTiO3)、鋯酸鋇(BaZrO3)、鈦酸鍶(SrTiO3)、鋯酸鍶(SrZrO3)、鈦酸鈣(CaTiO3)、鋯酸鈣(CaZrO3))的摻合物而製造。關於此點，表3之調配物將生成與表1之調配物所製造者大致相同的介電材料。
本發明之以上及其他特點在以下更完整地說明，且尤其是在申請專利範圍中指明，以下的說明詳述本發明之特定具體實施例，然而，其僅表示本發明原理可使用之各種方式中的少數。
1‧‧‧多層陶瓷片電容器
2‧‧‧介電層
3‧‧‧內部電極層
4‧‧‧外部電極
第1圖為本發明之一具體實施例的多層陶瓷片電容器之橫切面。
多層片電容器係藉由交錯堆疊介電層及內部電極以形成胚片而製造。在此感興趣的內部電極包含卑金屬，其包括鎳或鎳合金。形成該介電層之介電材料係以有機媒液系統，濕磨介電體成分而製造。將該介電組成物沈積在載體膜(如聚酯或聚丙烯)或帶(如不銹鋼)或 紙或基板(如氧化鋁或玻璃)上，塗覆該膜及形成片，將其與電極交錯堆疊而形成該胚片。
在形成胚片之後，藉由在空氣大氣中加熱到低於約350℃之溫度而移除有機媒液。一旦移除媒液，則將胚片在潮濕氮與氫之還原大氣(氧分壓為約10-12至約10-8atm)中，在約1100℃至約1400℃，較佳為約1200℃至約1350℃，更佳為約1225℃至約1325℃之溫度燒製。移除黏合劑及燒製片均可使用各種加熱廓線(heating profile)。
多層陶瓷電容器之組態在所屬技術領域為已知的。參考第1圖，其顯示多層陶瓷片電容器1之例示性結構。將電容器1之外部電極4配置在電容器片1之側面上，且電連接內部電極層3。電容器片1具有複數層交錯堆疊介電層2。電容器片1之形狀並不重要，雖然其經常為長方形。又大小並不重要，且該片可具有適合特定應用之尺寸，其一般為1.0至5.6毫米×0.5至5.0毫米×0.5至1.9毫米之範圍。堆疊內部電極層3使得其在對立端在片1之對立側面交錯暴露。即一組內部電極層3在片1之一側面暴露，而另一組內部電極層3在片1之對立側面暴露。將一外部電極4施加於電容器片1之一側面且電連接一組內部電極層3，且將另一外部電極4施加於片1之對立側面且電連接另一組內部電極層3。
本發明提供一種包含先質(其在燒製時形成包含摻雜至少鈣與鈦之鋯酸鋇鍶基質之介電材料)的混 合物之組成物。在一些具體實施例中，該混合物進一步包含先質，使得在燒製時生成進一步包含一種或以上的選自由硼與鎂所組成的群組之摻雜物之介電材料。由本發明之組成物所形成的介電材料呈現大於35，較佳為大於40，更佳為大於45之介電常數。
該介電層係由燒結包括鋇、鈣、鍶、鈦、與鋯之氧化物的摻合物(如表1或2)所形成的介電材料而形成。其可使用燒結助劑，包括B2O3與MgO。
另一途徑為以表3之鈦酸鋇、鋯酸鋇、鈦酸鍶、鋯酸鍶、鋯酸鈣、鈦酸鈣開始。只要提供所欲量之所欲金屬離子，上述氧化物之氫氧化物或其他形式，如碳酸鹽、乙酸鹽、硝酸鹽，及有機金屬化合物，如金屬甲酸鹽、草酸鹽等，具有相同的效果，對熟知此技藝者應為顯而易知。
該介電材料可有其他化合物，其條件為該其他化合物不負面影響介電性質。此化合物通常為原料中的雜質。
此介電組成物具有細微晶粒，其一般具有約0.5至約3微米之平均大小，較佳為小於約0.7微米之粒度。
各介電層具有至多約50微米之厚度。較佳為各介電層之厚度為約0.5微米至約50微米。更佳為各介電層之厚度為約2微米至約10微米。此組成物可用以製造具有薄介電層之多層陶瓷片電容器，以確保使用壽命期間之電容降解最小。在片電容器中堆疊的介電層數量通常為約2至約800，且較佳為約3至約400。
本發明之多層陶瓷片電容器係藉由使用糊以習知印刷及片化方法形成胚片，及燒製該胚片而製造。 在燒製後，將該片在如氧化鋁或氧化矽之介質中滾動乾燥而將角落修圓。其次，將含有例如銅之導電性糊塗佈於兩端以將暴露的內部電極連接在一起而封端。然後將該片終端在約800℃在氮大氣中燒製以在兩端將導體(例如銅)燒結成固態導電墊，而形成多層電容器。該終端為如第1圖所示的外部電極4。
介電糊。用以形成介電層之糊可藉由混合有機媒液與原始介電材料而得到，如在此所揭示。亦可使用先質化合物，其在燒製時轉化成此氧化物及複合氧化物，如以上所述。該介電材料係選擇含有這些氧化物之化合物、或這些氧化物之先質，及將其以合適的比例混合而得到。決定此化合物在原始介電材料中的比例而在燒製後可得到所欲的介電層組成物。該原始介電材料通常以平均粒度為約0.1至約3微米，且更佳為約1微米或以下之粉末形式使用。
有機媒液。有機媒液為黏合劑於有機溶劑中，或黏合劑於水中。在此使用的黏合劑之選擇並不重要；習知黏合劑，如乙基纖維素、聚乙烯基丁醇、乙基纖維素、與羥丙基纖維素，及其組合，連同溶劑為合適的。該有機溶劑並不重要，且可依照特定的施加方法(如印刷或片化)而選自習知有機溶劑，如丁基卡必醇、丙酮、甲苯、乙醇、二乙二醇丁基醚；2,2,4-三甲基戊二醇單異丁酸酯(Texanol®)；α-萜品醇；β-萜品醇；γ-萜品醇； 三癸醇；二乙二醇乙基醚(Carbitol®)、二乙二醇丁基醚(Butyl Carbitol®)、與丙二醇；及其摻合物。以商標名Texanol®銷售的產品得自田納西州Kingsport之Eastman Chemical Company；以商標名Dowanol®及Carbitol®銷售的產品得自密西根州Midland之Dow Chemical Co.。
對於各糊(介電或電極糊)之有機媒液含量無特定限制。該糊經常含有約1至5重量百分比之黏合劑、及約10至50重量百分比之有機溶劑，其餘為金屬成分(電極用)或介電成分(介電層用)。如果需要，則各糊可含有至多約10重量百分比之其他添加劑，如分散劑、塑化劑、介電化合物、及絕緣化合物。
內部電極。用以形成內部電極層之糊係藉由混合導電性材料與有機媒液而得到。在此使用的導電性材料包括導體，如在此所述的導電性金屬與合金，及各種在燒製時轉化成此導體之化合物，例如氧化物、有機金屬化合物、與樹脂酸鹽。
參考第1圖，形成內部電極層3之導體並不重要，雖然較佳為使用卑金屬，因為介電層2之介電材料具有抗還原性質。典型卑金屬包括鎳及其合金。較佳的鎳合金含有至少一種選自Mn、Cr、Co、Cu、與Al之其他金屬。較佳為含有至少約95重量百分比之鎳之合金。應注意，鎳及鎳合金可含有至多約0.1重量百分比之磷及其他微量成分(即雜質)。其可控制內部電極層之厚度以適應特定應用，但是該層一般為至多約5微米厚。較佳為內部電極層具有約0.5至約5微米，且更佳為約1至約5微米之厚度。
外部電極。形成外部電極層4之導體並不重要，雖然較佳為不昂貴的金屬，如銅、鎳、及任一或兩者之合金，視情況含有Mn、Cr、Co、或Al。其可控制外部電極層之厚度以適應特定應用，但是該層一般為至多約10至約50微米厚，較佳為約20至約40微米厚。用以形成外部電極之糊係藉與內部電極相同的方法製備。
然後可由介電層形成糊及內部電極層形成糊製備胚片。在印刷方法的情形，胚片較佳為藉由將該糊以積層形式交錯印刷在聚酯膜(例如聚對苯二甲酸伸乙酯(PET))基板上，將積層堆疊切割成預定形狀，及將其從該基板分離而製備。亦可使用片化方法，其中胚片係藉由從介電層形成糊形成胚片，將內部電極層形成糊印刷在各胚片上，及堆疊該印刷胚片而製備。在將有機媒液從胚片移除之後，將其燒製。有機媒液可在習知條件下，在空氣大氣中以0.01℃至20℃/小時，更佳為約0.03-0.1℃/小時之速率加熱，及保持在約150℃至約350℃，較佳為約200℃至約300℃，更佳為約250℃之溫度，歷時約30-700分鐘，較佳為約200-300分鐘之保持時間而移除。
燒製。然後將胚片在大氣中燒製，其係依照內部電極層形成糊中的導體型式而決定。若內部電極層係由卑金屬導體(如鎳及鎳合金)形成，則燒製大氣可具有約10-12至約10-8atm之氧分壓。其應避免在低於約10-12atm之分壓燒結，因為在此低壓，導體會不正常燒 結且可能從介電層分離。在高於10-8atm之氧分壓，內部電極層會被氧化。最佳為約10-11atm至約10-9atm之氧分壓。
為了燒製，將溫度從室溫提高到約1200℃至約1300℃，更佳為約1225℃之尖峰溫度。將溫度保持約2小時以強化稠化。更低的保持溫度無法提供充分的稠化，而更高的保持溫度會導致非常大的顆粒。燒製較佳為在還原大氣中進行。例示性燒製大氣包括潮濕N2、或N2與H2氣體的加濕混合物。燒結上升溫度速率為約50℃至約500℃/小時，較佳為約200℃至300℃/小時；保持溫度為約1225℃。保持時間為約0.5至約8小時，較佳為約1至3小時，更佳為2小時，及冷卻速率為約50℃至500℃/小時，較佳為約200℃至300℃/小時。
有機媒液移除及燒製可連續或分別進行。如果連續，則程序包括有機媒液移除，不冷卻而改變大氣，加熱到燒製溫度，在燒製溫度保持指定時間，然後冷卻。如果分別，則在有機媒液移除及冷卻之後將片溫提高到燒結溫度，然後將大氣改成還原大氣。
生成片可藉滾筒翻滾及/或噴砂而在端面拋光，例如在印刷或轉移外部電極形成糊及燒製形成外部電極(終端)之前。燒製外部電極形成糊可在乾燥氮大氣(氧分壓為約10-6atm)中，在約600℃至800℃進行約10分鐘至約1小時。
如果必要，則藉電鍍或所屬技術領域者已知的其他方法在外部電極上形成墊。本發明之多層陶瓷片電容器可例如藉焊接安裝在印刷電路板上。
[實施例]
以下實施例係提供以例證本發明之較佳態樣，且不意圖限制本發明之範圍。
概述。製備具有純鎳電極、10層有效層(各層為10至13微米厚)之多層陶瓷電容器，及在還原大氣(~10-10atm之pO2)中在1225℃燒結。進行物理及電測量。
[實施例1]
藉由將如表4所示的適量氧化物在水中研磨，而形成標記為樣品1之介電組成物。將粉末在具有1% Darvan® C(得自康乃迪克州Norwalk之RT Vanderbilt Co.,Inc.的聚合去凝劑)之1公升聚丙烯瓶中，使用2毫米YTZ(經氧化釔安定之氧化鋯)研磨成D50為約0.65微米之粒子。
藉習知手段將乾燥粉末粉碎而提供實施例1之介電粉末。
最終粉末具有0.3至1微米之平均粒度。然後將100克之以上粉末加入28.8克之包含聚乙烯基丁醇、甲苯、與乙醇之有機媒液，及濕磨24小時而製備帶式流延用漿液。將該濕漿液塗覆在聚酯膜上而形成介電胚帶。該介電胚帶之厚度為約15微米。使用習知鎳糊，將鎳電極藉習知網版印刷方法印刷在該乾燥介電胚帶上。堆疊總共10片，且在5100psi之壓力下及130 ℉(54℃)之溫度黏結形成胚片。切成合適的尺寸，使得在燒結及收縮(一般在X及Y方向均為15%至20%)之後片尺寸為約0.12”(L)×0.06”(W)(EIA1206大小)或0.08”(L)×0.05”(W)(EIA0805大小)，然後依照表5之燒盡循環將胚片加熱，而移除有機媒液。
對於實施例1，首先將片在約265℃之溫度移除其黏合劑，然後在pO2為~10-10atm之N2/H2/H2O的氣體混合物中，在1225℃之溫度燒結。該氣體混合物係將N2/H2氣體經由水溫為23℃之潤濕器加濕而得到。藉滾動將如此得到的片之角落修圓。將得自俄亥俄州Cleveland之Ferro Corporation的之外部電極形成銅糊TM50-081塗佈於端面，且在乾燥氮大氣中在775℃燒製約70分鐘，而形成外部電極。如此處理的多層電容器具有約3.2毫米×1.6毫米之尺寸(EIA1206大小)及變動厚度。介電層為9.7微米厚，及內部鎳電極層為約1.5微米厚。
由實施例1之粉末製造多層片電容器及測試。燒製條件及電性質歸納於表6。
所屬技術領域者易於得知額外的優點及修改。因此，本發明之廣義態樣不限於在此所示及說明的指定細節及例證性實施例。因而可進行各種修改而不背離一般發明概念之精神及範圍，如所附申請專利範圍及其等效物所定義。

Claims (11)

  1. 一種介電材料，其包含：26.5重量百分比至34.0重量百分比之BaO；18.0重量百分比至24.5重量百分比之SrO；41.0重量百分比至50.0重量百分比之ZrO2；0.50重量百分比至1.50重量百分比之CaO；及0.70重量百分比至2.50重量百分比TiO2。
  2. 如請求項1之介電材料，其進一步包含：0.01重量百分比至1.0重量百分比之B2O3；及0.01重量百分比至1.47重量百分比之MgO。
  3. 一種無鉛無鎘介電糊，其包含固體部分，其中該固體部分包含如請求項1之介電材料。
  4. 如請求項3之無鉛無鎘介電糊，其中該固體部分進一步包含至少一種選自由以下所組成的群組：0.01至1.0重量百分比之B2O3；0.01至1.47重量百分比之MgO；0.01至1.78重量百分比之H3BO3；及0.01至2.14重量百分比之Mg(OH)2。
  5. 一種形成電子組件之方法，其包含：將如請求項3或請求項4之介電糊塗佈於基板；及在足以燒結該介電糊之溫度下燒製該基板。
  6. 如請求項5之方法，其中該燒製係在1200℃至1350℃之溫度下進行。
  7. 一種多層陶瓷片電容器，其包含交錯堆疊以下之燒製 集合體：如請求項3或請求項4之介電糊之層；及包含Ag、Au、Pd、或Pt以外的過渡金屬之內部電極材料之層。
  8. 如請求項7之多層陶瓷片電容器，其中該內部電極材料包含鎳。
  9. 一種形成電子組件之方法，其包含：在基板上交錯塗佈以下之層：如請求項3或請求項4之介電糊，以形成至少一介電層；及含金屬電極糊，以形成至少一內部電極層；而形成積層堆疊；將該積層堆疊切割成預定形狀；將該經切割的堆疊從該基板分離；及燒製該堆疊而將該電極糊中的金屬稠化，及燒結該介電糊，其中該內部電極層及該介電層各具有層厚度。
  10. 一種無鉛無鎘介電組成物，其在燒製時形成如請求項1之介電材料，該介電組成物包含：47.8重量百分比至61.3重量百分比之BaZrO3；39.4重量百分比至53.6重量百分比之SrZrO3；及1.2重量百分比至3.6重量百分比之CaTiO3。
  11. 如請求項10之介電組成物，其進一步包含：0.1重量百分比至2.14重量百分比之Mg(OH)2；及0.1重量百分比至1.78重量百分比之H3BO3。
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Families Citing this family (3)

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KR102059804B1 (ko) * 2015-08-05 2019-12-27 페로 코포레이션 고유전 상수-k ltcc 유전성 조성물 및 장치
KR20190121137A (ko) 2018-08-06 2019-10-25 삼성전기주식회사 유전체 조성물 및 이를 이용한 전자 부품
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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110090619A1 (en) * 2005-09-28 2011-04-21 Ferro Corporation COG Dieletric Composition For Use With Nickel Electrodes

Family Cites Families (38)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1478809A (en) * 1975-11-11 1977-07-06 Standard Telephones Cables Ltd Monolithic cermic capacitors
US4379319A (en) 1982-02-18 1983-04-05 Ferro Corporation Monolithic ceramic capacitors and improved ternary ceramic compositions for producing same
US4540676A (en) 1984-05-23 1985-09-10 Tam Ceramics Low temperature fired dielectric ceramic composition with flat TC characteristic and method of making
JPS61275164A (ja) 1985-05-03 1986-12-05 タム　セラミツクス　インコ−ポレイテツド 誘電体セラミック組成物
US4816430A (en) 1987-06-09 1989-03-28 Tam Ceramics, Inc. Dielectric ceramic composition
US5258335A (en) 1988-10-14 1993-11-02 Ferro Corporation Low dielectric, low temperature fired glass ceramics
US5296426A (en) 1990-06-15 1994-03-22 E. I. Du Pont De Nemours And Company Low-fire X7R compositions
JP2605987B2 (ja) * 1991-02-19 1997-04-30 株式会社村田製作所 誘電体磁器組成物
US5601673A (en) 1995-01-03 1997-02-11 Ferro Corporation Method of making ceramic article with cavity using LTCC tape
US5661882A (en) 1995-06-30 1997-09-02 Ferro Corporation Method of integrating electronic components into electronic circuit structures made using LTCC tape
US5571767A (en) 1995-08-21 1996-11-05 Ferro Corporation Low fire X7R dielectric compositions and capacitors made therefrom
DE19546237A1 (de) 1995-12-12 1997-06-19 Philips Patentverwaltung Vielschichtkondensator mit Dielektrikum aus modifiziertem Bariumstrontiumtitanat
EP0844989B1 (en) 1996-06-14 2001-10-10 dmc2 Electronic Materials B.V. Ceramic multilayer capacitor
US6043174A (en) 1997-06-26 2000-03-28 Mra Laboratories High dielectric constant X7R ceramic capacitor, and powder for making
JP3305626B2 (ja) 1997-07-22 2002-07-24 太陽誘電株式会社 誘電体磁器組成物とこの誘電体磁器組成物を用いたセラミック電子部品
DE19737324A1 (de) 1997-08-28 1999-03-04 Philips Patentverwaltung Vielschichtkondensator mit silber- und seltenerdmetalldotiertem Bariumtitanat
JP3586148B2 (ja) * 1998-09-30 2004-11-10 Ｔｄｋ株式会社 非還元性誘電体磁器材料およびその製造方法ならびに積層磁器コンデンサ
US6185087B1 (en) 1999-04-08 2001-02-06 Kemet Electronics Corp. Multilayer ceramic chip capacitor with high reliability compatible with nickel electrodes
JP3642282B2 (ja) * 2000-02-09 2005-04-27 松下電器産業株式会社 誘電体磁器組成物とこれを用いた積層セラミックコンデンサ
US6723673B2 (en) 2000-08-31 2004-04-20 Mra Laboratories, Inc. High dielectric constant very low fired X7R ceramic capacitor, and powder for making
KR100444230B1 (ko) * 2001-12-27 2004-08-16 삼성전기주식회사 내환원성 유전체 자기 조성물
JP3992647B2 (ja) 2003-05-28 2007-10-17 Ｔｄｋ株式会社 抵抗体ペースト、抵抗体および電子部品
TWI287811B (en) * 2005-02-04 2007-10-01 Murata Manufacturing Co Multilayer ceramic capacitor and method for manufacturing the same
US7230817B2 (en) 2005-04-15 2007-06-12 Ferro Corporation Y5V dielectric composition
US7161795B1 (en) 2005-09-26 2007-01-09 Ferro Corporation COG dielectric composition for use with copper electrodes
CN101272991B (zh) * 2005-09-28 2012-01-18 费罗公司 用于与镍电极一起使用的cog电介质组合物
US7547369B2 (en) 2006-08-31 2009-06-16 Ferro Corporation Method of making multilayer structures using tapes on non-densifying substrates
CN101583579B (zh) 2006-11-30 2012-12-05 韩国窑业技术院 无玻璃微波介电陶瓷及其制法
US7541306B2 (en) 2007-01-17 2009-06-02 Ferro Corporation X8R dielectric composition for use with nickel electrodes
US7521390B2 (en) 2007-03-05 2009-04-21 Ferro Corporation Ultra low temperature fixed X7R and BX dielectric ceramic composition and method of making
CN101848879B (zh) 2007-11-06 2013-08-14 费罗公司 无铅无镉的、低温烧成的x7r介电陶瓷组合物及制备方法
CN101607819B (zh) * 2009-07-17 2012-01-25 苏州达方电子有限公司 介电陶瓷组合物及其所制成的积层陶瓷电容器
CN103124707A (zh) * 2011-01-21 2013-05-29 株式会社村田制作所 层叠陶瓷电容器及层叠陶瓷电容器的制造方法
KR101632589B1 (ko) * 2012-08-09 2016-06-22 가부시키가이샤 무라타 세이사쿠쇼 적층 세라믹 콘덴서 및 그 제조방법
KR102064008B1 (ko) 2013-01-15 2020-02-17 삼성전기주식회사 적층 커패시터, 적층 커패시터가 실장된 기판
KR101565645B1 (ko) * 2013-07-11 2015-11-03 삼성전기주식회사 적층 커패시터 소자
US9704650B2 (en) 2013-10-30 2017-07-11 Ferro Corporation COG dielectric composition for use with nickel electrodes
JP6438594B2 (ja) 2015-02-27 2018-12-19 フエロ コーポレーション 低誘電率及び中誘電率ｌｔｃｃ誘電体組成物及び装置

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110090619A1 (en) * 2005-09-28 2011-04-21 Ferro Corporation COG Dieletric Composition For Use With Nickel Electrodes

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