TWI290096B - Method for making raw ceramic powder, raw ceramic powder, dielectric ceramic produced using raw ceramic powder, and monolithic ceramic electronic component using dielectric ceramic - Google Patents

Method for making raw ceramic powder, raw ceramic powder, dielectric ceramic produced using raw ceramic powder, and monolithic ceramic electronic component using dielectric ceramic Download PDF

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Publication number
TWI290096B
TWI290096B TW091110724A TW91110724A TWI290096B TW I290096 B TWI290096 B TW I290096B TW 091110724 A TW091110724 A TW 091110724A TW 91110724 A TW91110724 A TW 91110724A TW I290096 B TWI290096 B TW I290096B
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Taiwan
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ceramic
powder
metal
dielectric
ceramic powder
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TW091110724A
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English (en)
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Koji Hattori
Shinsei Okabe
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Murata Manufacturing Co
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Description

1290096
本發月有關-種製造陶竟粉末原料之方法、陶竟粉末原 料、利用料粉末原料製得之介電„、以及㈣該介電 陶兗的單片陶瓷電子元件。 景拮街 隨著單片陶t電容器的小型化，介電H層厚度已減小 到接近約3微米。亦已實現使用賤金屬，例如Cu*Ni，作爲 内部導體（内電極）原料。近期，達成了層厚度進—步減小 且開發出厚度接近1微米之介電陶瓷層。 製造此種單片陶瓷電容器的介電原料時，在基劑陶瓷粉 末中經常加入多種金屬元素，例如鈦酸鋇粉末，其目的為 改變電特性和改善可燒結性。添加此種金屬元素至基劑陶 瓷粉末中之已知方法實例如下： (1) 將添加金屬元素的碳酸鹽或氧化物或其混合物添加 於介電陶瓷之基劑粉末中，混合，然後瑕燒之方法； (2) 將含添加金屬元素的水溶液添加於介電陶瓷基劑粉 末淤漿中，於其中添加沈澱劑使其沈澱，過濾並乾燥，然後 嘏燒之方法； (3) 於介電陶瓷基劑粉末中添加黏合劑及含添加金屬元 素化合物的溶液，形成於漿，用刮刀方法或類似方法形成 生片（green sheet)，然後燒製之方法（參見日本未審查專 利申請公開號5-89724和5-1443J9);及 (4) 將介電陶瓷基劑粉末、有機溶劑和表面活性劑混合， -4- ^紙張尺度適用中國國家標準(CNS) A4規格(210X 297公釐） 1290096 A7 B7 五、發明説明（2 ) 並研磨成淤漿，於淤漿中添加含添加金屬元素的複合烧醇 鹽溶液’除去有機溶劑後得到表面被含添加金屬元素的複 合烷醇鹽塗覆的陶瓷基劑粉末顆粒，然後煆燒之方法（參見 曰本未審查的專利申請公開號10-139553)。 由於方法（1)中的粉末彼此混合，無法在顯微水平將基劑 粉末中的添加金屬元素之礙酸鹽或氧化物均勻分散。所以 ，由於添加的金屬元素在陶瓷基劑粉末中分離，因此基劑 粉末各顆粒的添加效果不同，增加了陶瓷電子元件特性間 的差異，亦難以獲得所需特性。 上述方法（2)中’儘管與方法（1)相比有所改善，仍不具 備足夠的可分散性，且無法藉一種類型的沈澱劑將多種金 屬離子一起沈澱。例如，儘管可藉與碳酸鹽離子反應將Sr+2, Ca+2和Mg+2以複合碳酸鹽形式沈澱，但碳酸鹽離子無法使 Ti “等沈澱。 必須使用不含金屬的銨鹽作爲沈澱劑，因爲Zn+2, Mn+2, Ni+2，Co+2等離子形成可溶的胺複合物而不會沈澱。 上述方法（3)中，有機黏合劑依淤漿形成過程中存在的陰 離子或陽離子種類而形成膠體，因爲黏合劑與該等離子有 相互作用，並因此不可能均勻分散添加劑。 方法（4)中，可抑制黏合劑的膠凝過程，因爲在基劑粉末 顆粒表面被含添加金屬元素吟複合烷醇鹽塗覆之後進行烺 燒’接著於其中添加黏合劑溶液形成於衆。然而，瑕燒期 間，添加於用以改變電特性的舍屬元素化合物及用以改善 可燒結性的形成玻璃的金屬元素化合物被分解。改變電特 -5- 本紙張尺度適用中國國家標準(CNS) A4規格(210X 297公釐) 1290096
性的成分較好與玻璃成分反應，結果不可能獲得滿意的特 性修飾效果，或可改變玻璃的軟化溫度，因此無法充分實 現其作爲燒結助劑的功能。上述方法（1)和（3)中亦存在相 同問題0 發明概诚 本發明一目的係提供一種陶瓷粉末原料及製造此陶瓷粉 末原料之方法，該方法中改變電特性的金屬化合物（以下稱 ”電特性改質劑"）及改善燒結性的金屬化合物（以下稱"燒 結助劑"）形成於陶瓷基劑粉末各顆粒表面，而不損及其作 爲電特性改質劑和燒結助劑的功能。本發明另一目的係提 供一種使用陶瓷粉末原料製造之介電陶瓷及使用該介電陶 瓷的單片陶瓷電子元件。 本發明一方面中，製造陶瓷粉末原料之方法包括如下步 驟：混合和研磨作爲陶瓷粉末原料主要成分的基劑粉末、 有機溶劑、溶於有機溶劑且含改變基劑粉末電特性的金屬 元素之第一種有機金屬化合物、以及溶於有機溶劑且含改 善基劑粉末燒結性的金屬元素的第二種有機金屬化合物， 以形成淤漿；從淤漿去除有機溶劑獲得基劑粉末，該基劑 粉末顆粒表面經第一種有機金屬化合物及第二種有機金屬 化合物塗覆；然後在高於第一種有機金屬化合物分解溫度 但低於第二種有機金屬化合物分解溫度的溫度下熱處理該 基劑粉末。 較好’於於漿中添加表面活铁劑。亦較好，第一種有機 金屬化合物爲金屬烷醇鹽、金屬乙醯丙酮酸鹽或金屬皂之 -6 - 本纸張尺度適用中國國家標準(CNS) Α4規格(210X297公爱) 1290096
至少一種。 第二種有機金屬化合物較好爲由矽溶膠、金屬乙酸鹽和 多經基醇反應所形成的複合金屬烷醇鹽。 本發明另一方面中，陶瓷粉末原料包含作爲陶瓷粉末原 料主要成分的基劑粉末、含改變基劑粉末電特性的金屬元 素之第一種有機金屬化合物、及含改善基劑粉末燒結性的 金屬元素之第二種有機金屬化合物，該第一及該第二種有 機金屬化合物附著在基劑粉末顆粒表面，該基劑粉末在高 於第一種有機金屬化合物分解溫度且低於第二種有機金屬 化合物分解溫度的溫度下進行熱處理。 較好，基劑粉末為BaxTi02+x粉末，其中100 < χ < 1〇3 。較好’基劑粉末晶體之c轴/a轴比率約1()〇3至1〇1。又 較佳，基劑粉末平均粒徑約50至200 nm，且最大粒徑約300 nm 或更小。 本發明又一方面中，藉燒製陶瓷粉末原料而製造介電陶 本發明再一方面中，單片陶瓷電子元件包括積層物，該 積層物包括多個介電陶瓷層和多個沿著介電陶瓷層間預定 介面延伸的内部電極，該内部電極的放置使得被介電陶瓷 層分開的兩個相鄰内部電極之間形成電容，介電陶瓷層則 由上述介電陶瓷所組成。 較好，内部電極含有賤金屬作爲主要成分。更好，賤金 屬為錄或鎳合金。再者，放置杳兩個相鄰内部電極間的介 電陶瓷層厚度較好約1微米或更薄。 本紙張尺度適用中國國家標準(CNS) A4規格(210X297公爱) 1290096 A7 B7
邇^簡單說明 圖1爲本發明一具體例之單片陶瓷電容器截面圖； 圖2爲顯示本發明一具體例之有機複合烷醇鹽的熱分解 溫度之TG-DTA圖；及 圖3爲顯示本發明一具體例之含辛酸鹽金屬皂之混合溶 液熱分解溫度之TG-DTA圖。 較佳真艚例說明 本發明中，製造陶瓷粉末原料之方法包括如下步驟：混 合和研磨作爲陶瓷粉末原料主要成分的基劑粉末、有機溶 劑、溶於有機溶劑且含改變基劑粉末電特性的金屬元素的 第一種有機金屬化合物、以及溶於有機溶劑且含改善基劑 粉末燒結性的金屬元素的第二種有機金屬化合物，以形成 淤漿；從淤漿中去除有機溶劑獲得基劑粉末，該基劑粉末 顆粒表面被第一種有機金屬化合物及第二種有機金屬化合 物塗覆；然後在高於第一種有機金屬化合物分解溫度且低 於第二種有機金屬化合物分解溫度的溫度下熱處理基劑粉 改變電特性的金屬元素實例包含Co、Ni、Mn、Mg、Ba、 Ca、Y及稀土元素，例如Ce、Nd、Er及Dy。改善燒結性的金 屬元素實例包括Li、Si、Ca、Ba、Sr及Ti。 根據本發明製造陶瓷粉末原料之方法中，首先，藉混合 和研磨陶瓷基劑粉末、第一和第二種有機金屬化合物以及 有機溶劑獲得淤漿，該淤漿中棊劑粉末可良好地研磨成粉 並分散。若又混合有表面活性劑並研磨於其中，該表面活 -8- 本紙張尺度適用中國國家標準(CNS) A4規格(210X297公釐) 1290096 A7 B7 五、發明説明（6 ) 性劑將吸附在粉末顆粒表面。 藉除去淤漿中的有機溶劑，該第一和第二種有機金屬化 合物可以均勻地黏附在基劑粉末各顆粒表面上。 藉由在高於第一種有機金屬化合物分解溫度、低於第二 種有機金屬化合物分解溫度的溫度下熱處理生成的粉末， 該第一種有機金屬化合物，亦即改變電特性的金屬元素化 合物’予以分解、分散並以細顆粒形式沈澱在基劑粉末顆 粒表面。分解之第一種有機金屬化合物亦部分擴散進基劑 粉末顆粒之表面層。另一方面，第二種有機金屬化合物， 亦即改善燒結性的金屬元素化合物，並未分解且仍均勻地 黏附在陶瓷粉末原料顆粒表面。 當使用所製得之陶瓷粉末原料製造介電陶瓷時，分解的 第種有機金屬化合物在燒製步驟中均勻地熱擴散於基劑 粉末中，從而改善該介電陶瓷特性。在此階段，第二種有 機金屬化合物在預定燒結溫度分解形成玻璃，並因此加速 陶瓷燒結。 所用表面活性劑並無特殊限制，可單獨或組合使用已知 的表面活性劑。表面活性劑典型實例包括離子型表面活性 劑例如幾酸鹽、〜酸鹽、硫酸醋鹽、碟酸g旨鹽、脂肪族 胺|及其錢鹽、芳香族季錄鹽和雜環季錢鹽；非離子表面 活性劑，例如聚氧乙敎㈣、單分散聚氧乙埽二級醇鍵 、聚氧乙烯垸基苯基_、聚氧乙稀縮水甘油脂肪酸醋、聚 氧？烯山梨糖醇酐脂肪酸酯、翏氧乙二醇脂肪酸酯、聚丙 二醇㈣㈣ '脂㈣垸醇醯胺及聚氧乙料基胺；以及 1290096 A7 B7 五、發明説明（7 ) 兩性表面活性劑，例如羧基甜菜鹼、磺基甜菜鹼、胺基叛 酸鹽及咪唑啉衍生物。 至於第一種有機金屬化合物，較好，可使用至少一種選 自金屬烷醇鹽、金屬乙醯丙酮酸鹽及金屬皂之化合物。至 於金屬烷醇鹽，可將各含單一金屬元素的烷醇鹽分別加入 基劑粉末中或可使用複合烷醇鹽。至於金屬皂，宜使用已 知金屬皂，例如辛酸鹽或環烷酸鹽。 至於第二種有機金屬化合物，較好使用由矽溶膠、金屬 乙酸鹽和多元醇反應形成的複合金屬燒醇鹽。此複合金屬 烧醇鹽與含單一金屬元素的烷醇鹽相比更耐潮氣，且因此 可防止水解産生的不溶化合物。因此，該原料易於處理。 藉使用石夕溶膠作爲合成複合金屬烧醇鹽的初始原料，可 以避免組成改變。亦即，由於使用低沸點和高揮發性的化 合物例如四乙基矽酸鹽作爲初始原料時，發生^成分的揮 發和汽化造成送料階段和最終階段間的組成差異可以避免。 第二種有機金屬化合物之較好實例包含例如 Li2〇-BaO-Si02-為主之化合物，該化合物含有在約i，〇〇〇°c 或更低的溫度下可轉變爲液態玻璃之金屬元素種類和數量。 本發明之陶瓷粉末原料包括作爲陶瓷粉末原料主要成分 的基劑粉末、含改變基劑粉末電特性的金屬元素之第一種 有機金屬化合物、及含改善基劑粉末燒結性的金屬元素之 第一種有機金屬化合物，該第一及第二種有機金屬化合物 附著在基劑粉末顆粒表面，該棊劑粉末在高於第一種有機 金屬化合物分解溫度且低於第二種有機金屬化合物分解溫 -10- 本紙張尺度適用中國國家標準(CNS) A4規格(210X297公釐) 1290096 A7 B7 五、發明説明（8 ) 度的溫度下進行熱處理。 至於基劑粉末，可使用通式爲AB〇3的化合物，其中A爲至 少一種二價金屬，例如選自Ba、（^及Sr所成組群，B爲至少 一種四價金屬，例如選自^及計所成組群。其典型實例爲 具有四方鈣鈦礦結構的i 〇2+χ氧化物，且特別地，爲了 獲得非還原四方鈣鈦礦結構的氧化物，下標χ較好約1〇〇 至1· 03。爲了改善鐵電性，亦即增加介電常數，基劑粉末 晶體之c軸/a軸比率較好約1. 〇03至〇1。 當使用所得陶瓷粉末原料作爲單片陶瓷電容器的介電材 料時，該電容器包括厚度爲1微米或更薄的介電陶瓷層，較 好基礎陶瓷粉平均粒徑約50至200 nm，且最大粒徑約3〇〇 μ 或更小。若平均粒徑小於約50 nm，則與添加成分的反應過 強’且燒結的介電陶瓷粒徑過大，導致介電常數—溫度性質 增加，而不佳。若平均粒徑超過約2〇〇 nm ,則與添加成分 的反應將減少，導致難以修飾其特性。若基劑陶瓷組合物 粉末含有最大粒徑超過約300 nm的顆粒，當使用此陶兗粉 末原料製造介電陶瓷時，可靠性會降低。 本發明介電陶瓷藉燒製陶瓷粉末原料而製造。 本發明之單片陶瓷電子元件包括積層物，其包含多個介 電陶瓷層和多個沿著介電陶瓷層間預定介面延伸的内電極 ，該等内部電極的放置使得被一或多個介電陶瓷層分開的 兩個相鄰内部電極間形成電容，介電陶瓷層則由上述介電 陶瓷所組成。單片陶瓷電子元件的内部電極較好包 鎳合金作爲主要成分。 I__^_-11-__ 本紙張尺度適用中國國家標準(CNS) A4規格(21()><297公爱） -------- 裝 訂
T290096
#圖1為圖示單片陶瓷電容器的截面圖，該電容器爲本發明 單片電子疋件之一實例。單片陶瓷電容器j包括積層物4, 該：層物包括多個彳電陶瓷層2及多個沿著彳電陶瓷層2間 預定介面延伸的内部電極3。内部電極3的放置使得其間有 個介電陶瓷層2的兩個相鄰内電極3之間形成電容。 外部電極5形成在積層物4兩側。該外部電極5與特定内部 電極3為電連接。與積層物4一側的外部電極5電連接的内部 電極3及與另一側的外部電極5電連接的内電極3交替排列 在積層物4上。 早片陶瓷電容器1中，介電陶瓷層2由本發明的介電陶瓷 組成。 /基於成本考量，内部電極3較好由鎳或鎳合金作爲主要成 分所組成。外部電極5可藉例如將含B2〇3-Li2〇_Si〇2 —Ba〇為 主的玻璃粉之Ag漿糊塗敷在積層物4兩側，隨後在還原氣氛 下烘焙而形成。 (可溶於有機溶劑且包含改善燒結性之金屬元素之第二 種有機金屬化合物之合成） 首先’犁備乙酸鋰、乙酸鋇、乙酸鈣和乙酸鰓作爲起始 物’並稱重以滿足下表1所示各金屬原子的莫耳比❶因而製 備之起始物添加於預先裝有有機溶劑三羥基丙烷（THp)的 燒杯中，加熱到200 Ό使其溶解，從而開始反應。反應完成 後’溶液冷卻至室溫，並添加令溶膠和異丙氧化欽，以滿
1290096 A7 ___B7_ 五、發明説明（" 足表1中所示各金屬原子莫耳比。然後加熱到200°C以産生 第二種有機金屬化合物溶液。 爲了找出所得第二種有機金屬化合物的熱分解溫度，藉 TG - DTA進行熱分析。結果參見圖2。如圖所示，第二種有機 金屬化合物的分解溫度約465°C。 表1 Si Li Ba Ca Sr Ti 1· 00 1. 20 0· 16 0· 12 0. 12 0. 08 (陶瓷粉末原料之製作） 首先，藉水解方法生成作爲基劑粉末的BaTi03粉末，該 粉末為陶瓷粉末原料的主要成分。所得粉末平均粒徑爲 19 nm，並在多種熱處理條件下熱處理該粉末，得到表2所 示之BaTi03粉末，該BaTi03粉末有多種平均粒徑及晶體之c 轴/a轴比例。在熱處理過程中聚集的粉末顆粒在熱處理後 予以研磨。 粒徑藉掃描電子顯微鏡測量。至於晶體之c轴/a轴比例， 進行X -射線繞射分析’結果使用Rietveld分析進行X_射線 輪廓套入以確定晶格常數。 表2 BaTi03 熱處理溫度 熱處理後的 c轴/a轴比例 粉末類型 (°C ) 平均粒徑（nm) A 600 63 1. 003 B 800 ^ 85 1. 006 C 900 117 1. 008 -13 - 本紙張尺度適用中國國家標準(CNS) A4規格(210X297公釐) 1290096
----- D 1，000 146 1· 009 S 2Μ. '«Λ? 一，》 素之第種有機金屬化合物，將含Mg、Μη、Dy和Ba辛酸班 之金屬息’其量相對於1〇〇莫耳BaTi〇3分別爲1〇、〇5、^ =丨.〇莫耳，加入50g的各BaTi〇3粉末中。再於其中添加先 前獲得的第二種有機金屬化合物，其量以氧化物計，爲 BaTi〇3重量的2%。所得混合物、作爲有機溶劑的4〇毫升甲 苯以及300克作爲混合介質的部分穩定化且直徑爲2亳米之 氧化鍅小球放置於500 cc聚乙烯杯中，混合及研磨8小時。 所得淤漿轉移至旋轉蒸發器，並置於7〇。〇水浴中。在託 至30 minHg下減壓蒸餾除去有機溶劑，從而對各類型得到 BaTi〇3粉（基劑粉末），該粉末顆粒表面被第一和第二種有 機金屬化合物塗覆。 所得BaTi〇3粉在200至500 Ό的電爐中熱處理而製造每種 A-D類型的陶瓷粉末原料。 爲了檢驗辛酸鹽金屬皂（作爲第一種有機金屬化合物）的 熱分解溫度’以TG-DTA進行熱分析。結果參見圖3。如圖所 不’含辛酸鹽金屬息的混合溶液分解溫度約爲250。 (單片陶瓷電容器的製造及評估） 將聚乙婦縮丁搭為主之黏合劑（相對陶竟粉末原料重量 為7· 5%)、增塑劑（相對陶瓷粉末原料重量為2· 5%)和甲苯 (相對陶瓷粉末原料體積為兩倍）添加於陶竞粉末原料中， 並在一個另加入300克部分穩定化且直徑2毫米的氧化結小 球作爲混合介質的500 cc聚乙烯杯中，混合及分散16小時 -14- 本紙張尺度適用中國國家標準(CNS) A4規格(210 X 297公釐) 1290096 A7 _____B7 五、發明説明（12~)~~一 "" " ^ ’以製造陶瓷淤漿。採用刮刀法將該陶瓷淤漿製成薄片， 如此製出厚度〇·8微米的矩形生片。接著，將含有鎳爲主要 成分的導電漿料印在生片上，形成用於組成内部電極的導 電漿膜。 將所得多個陶瓷生片層壓，使暴露導電漿層的邊緣交替 面向積層物不同側面。積層物在Ν2氣及350 Γ下加熱除去黏 合劑，然後在還原氣氛中於930至990°C燒製2小時，該還原 氣體包括H2、N2和氧分壓爲10-9至10-12 *^3的1120。 在燒結之積層物兩側塗敷含B2〇3-Li2〇-Si02-BaO為主之 玻璃料的Ag漿糊，並在N2氣中在60(TC烘焙，從而形成與内 部電極電相連的外部電極。 所製得的單片陶瓷電容器外部尺寸爲：寬5· 〇亳米、長5.7 毫米、厚2· 4毫米，放入内部電極間的介電陶瓷層厚度爲〇5 微米。有效介電陶瓷層總數爲5,且每層反電極面積爲16 3 X 10-6 m2。 · 接著，對各樣品100個測試片測量電特性。計算由於短路 等原因而無法評估特性的測試片數量，並計算故障率。 依照JIS C5101-10採用自動橋型儀錶測量電容（c)和介 電損失（tan δ)，並以測量的電容爲基礎計算介電常數 (Ο 〇 用絕緣阻抗檢測器，藉施加5 V的直流電壓2分鐘測定 25Ό之絕緣阻抗（R)，並計算電阻係數。 -15- 本紙張尺度適用中國國家標準(CNS) Α4規格(210X297公釐) 1290096 A7 B7 13 五、發明説明（ 至於電容隨溫度的改變速率，測量20Ό的電容在-25Ό 至+85Ό間之變化率（△ c/C2〇)& 25<c的電容在-55t：至 + 125Ό間之變化率（△ C/C25)。 爲了測量擊穿電壓，採用電壓增加速率爲100 V/sec的直 流電壓。 间溫負載測試中，在1 50eC施加5 V的直流電壓測量各測 試片絶緣阻抗（R)隨時間的變化，絕緣阻抗（R)達到丨〇5 Ω 或更低之點定義爲失效。測量達到失效的平均壽命。 測量結果示於表3及4。表3及4中，標記星號的樣品不在 本發明範圍内。 表3 樣品號 BaTiOa 熱處理溫度 燒製溫度 缺陷率 電阻係數 粉末類型 (°C) (°C) (%) (Ω · cm) 1 A 300 950 1 13· 0 2 B 300 950 0 13. 1 _3 C 300 950 5 13· 1 4 D 300 950 9 13· 2 *5 B 200 950 84 11· 1 6 B 400 950 0 13· 1 氺7 B 500 950 0 13· 1 8 B 400 930 0 12· 8 9 B 400 960 0 13. 1 10 B 400 990 3 13· 0 -16- 本紙張尺度適用中國國家標準(CNS) Α4規格(210 X 297公釐) 1290096 A7 五、發明説明
_表4 樣品號 介電 介電 電容隨溫度之 擊穿 平均 常數 損失 變化率 電壓 壽命 (%) 85°C 125°C (kV/mm) (hr) (%) (%) 1 1，210 2. 6 -9· 8 -14. 0 81 85 2 1，170 2· 8 -9· 7 -13· 8 88 91 3 1，310 2· 5 -9· 5 -13· 8 84 101 4 1，870 2.4 -9· 4 -13. 7 77 86 *5 - 一 一 6 l,JJ70j 2· 7 -9, 5 -14· 0 88 一 ·| 丨1 · 一· 一 90 氺7 960 3· 1 -8· 2 -28· 6 65 10 8 1，140 3. 1 -9· 8 -15. 0 91 76 9 1，200 2· 7 -9· 6 -13· 8 85 88 10 1，510 2.4 -9· 8 -14. 7 81 86 在5號樣品之例中，熱處理溫度爲200Ό，該溫度低於第 一種有機金屬化合物的分解溫度（25(rc )，該第一種有機金 屬化合物可溶於有機溶劑且含改變基劑粉末電特性的金屬 元素，因爲在有機金屬化合物中的有機成分分解時産生氣 體，所以在燒製時出現介電陶瓷組分的結構缺陷，且内部 電極的金屬顆粒進入該缺陷，從而易於發生短路。 7號樣品之例中，熱處理溫度爲5〇(rc，該溫度高於第二 種有機金屬化合物的分解溫度（、465Ό )，該第二種有機金屬 化合物可溶於有機溶劑且包含改善基劑粉末燒結性的金屬
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線 -17-本纸張尺度適用中國國家標準(CNS) Α4規格(210 X 297公董) 1290096 A7 B7 15 五、發明説明（ 疋素，第一種有機金屬化合物和爲了低溫燒結而加入的第 二種有機金屬化合物分解産生的物質形成玻璃相，且在基 劑粉末中無法充分溶化，導致電容隨溫度之變化率增加且 平均壽命減少。 相反，本發明範圍内的1至4、6及8至10號樣品的缺陷率 低，且單片陶瓷電容器顯示優異電特性，例如電容隨溫度 之改變率及平均壽命。 顯而易見，如上所述，根據本發明之製造陶瓷粉末原料 方法可以提供一種陶瓷粉末原料，其中一種改變電特性的 金屬化合物（電特性改質劑）和一種改善燒結性的金屬化合 物（燒結助劑）形成於陶瓷基劑粉末各顆粒表面，但不損及 其作爲電特性改質劑和燒結助劑的功能。 藉由使用此種陶竟粉末原料，甚至在介電陶竟層薄到其 厚度爲1微米或更小時’均可製造出單片電容器作爲單片陶 瓷電子元件。因此’可以高度可靠地製作大容量的小型化 單片陶瓷電容器。 -18- 本紙張尺度適用中國國家標準(CNS) A4規格(210 X 297公釐)
裝 訂

Claims (1)

  1. A8 B8 129Ο®9)6i 110724號專利申請案 g申請專利範圍里楚^96年2月卷 修正本頁 丨4^"告本^ 1. 一種改質陶瓷粉末原料之製造方法 提供-種淤漿’該於漿包括陶曼趴：括： 爲含金屬的電特性改質劑之第一 77末原料、可熱分解 熱分解爲含金屬的燒:结助劑之第有機金屬化合物、可 、及可溶解第一和第二種有機金屬:種人有機金屬化合物 從於漿中除去有機溶劑獲得基:物之有機溶劑； 括以第-和第二種有機金屬化合二’該基劑粉末包 料顆粒；及 塗覆的陶瓷粉末原 在高於第一種有機金屬化合物分 有機金屬化合物分解溫度的溫度下埶：-、低於、第二種 其中第一種有機金屬化合物‘自、：】基劑粉末’ 乙酿丙嗣酸鹽及金屬息之至少烧醇鹽、金屬 二：金屬化合物為们容膠、金屬乙酸鹽及多元 知之稷5金屬烷醇鹽反應産物；且 陶瓷粉末原料為介電陶瓷粉末原料。 2. 如：：專利範圍第i項之改質陶兗粉末原料之製造方法 ，/、中淤漿又包括表面活性劑。 法，其中該陶竟粉末包MaJi0其中i00 S 1.03 3_如申請專利範圍第i項之改質陶竟粉末原料之製造方 < 4·如申請專利範圍第3項之改質陶兗粉末原料之製造方 法其中陶变粉末晶體之e^/a軸比例爲約1〇〇3至1〇1。 5.如申凊專利範圍第4項之改質陶瓷粉末原料之製造方 法，其中该陶瓷粉末之平均粒徑約5〇至2〇〇 nm及最大 78468-960209.doc • 1 _ ^紙張尺度適用t S ®家鮮(CNS) A4規格(21GX 297公^
    、申請專 利範圍 l29〇〇96 或更小 6· 教復爲約3〇〇 多嶋子元件，包括一積層物，該積層物包括 的内；雷：瓷層和多個沿著介電陶瓷層間的介面延伸 開的亟°亥内邛電極係放置使得由介電陶瓷層所分 ]的兩個相鄰内部電極之間形成電容， 瓷介電陶瓷層包括如申請專利範圍第1項之改質陶 di:料之製造方法燒製所得之介電陶竟。 雷k 項之早片陶瓷電子元件，其中内部 电極包括賤金屬。 卜專利乾圍第6項之單片陶瓷電子元件，其中賤金 屬為鎳或鎳合金。 9.:申請專利範圍第6項之單片陶瓷電子元件，其中排列 :兩個相鄰内部電極間之介電陶竟層厚度爲m米或更 溥。 78468-960209.doc ·2· 本紙張尺度適用中國國家標準(CNS) Α4規格(210X 297公愛)
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