TWI427051B - 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 PDFInfo
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- TWI427051B TWI427051B TW100108800A TW100108800A TWI427051B TW I427051 B TWI427051 B TW I427051B TW 100108800 A TW100108800 A TW 100108800A TW 100108800 A TW100108800 A TW 100108800A TW I427051 B TWI427051 B TW I427051B
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- 239000000919 ceramic Substances 0.000 title claims description 79
- 239000003985 ceramic capacitor Substances 0.000 title claims description 35
- 229910052720 vanadium Inorganic materials 0.000 claims description 25
- 239000003990 capacitor Substances 0.000 claims description 15
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 7
- 229910052691 Erbium Inorganic materials 0.000 claims description 4
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 4
- 229910052689 Holmium Inorganic materials 0.000 claims description 4
- 229910052765 Lutetium Inorganic materials 0.000 claims description 4
- 229910052771 Terbium Inorganic materials 0.000 claims description 4
- 229910052775 Thulium Inorganic materials 0.000 claims description 4
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 4
- 229910052727 yttrium Inorganic materials 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- 229910052693 Europium Inorganic materials 0.000 claims description 3
- 229910052779 Neodymium Inorganic materials 0.000 claims description 3
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 3
- 229910052772 Samarium Inorganic materials 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- 238000010030 laminating Methods 0.000 claims description 2
- 239000000843 powder Substances 0.000 description 30
- 239000002245 particle Substances 0.000 description 20
- 239000002994 raw material Substances 0.000 description 16
- 230000007547 defect Effects 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 9
- 238000000034 method Methods 0.000 description 7
- 230000002950 deficient Effects 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 101100513612 Microdochium nivale MnCO gene Proteins 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 206010021143 Hypoxia Diseases 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 150000002902 organometallic compounds Chemical class 0.000 description 2
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/018—Dielectrics
- H01G4/06—Solid dielectrics
- H01G4/08—Inorganic dielectrics
- H01G4/12—Ceramic dielectrics
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/018—Dielectrics
- H01G4/06—Solid dielectrics
- H01G4/08—Inorganic dielectrics
- H01G4/12—Ceramic dielectrics
- H01G4/1209—Ceramic dielectrics characterised by the ceramic dielectric material
- H01G4/1218—Ceramic dielectrics characterised by the ceramic dielectric material based on titanium oxides or titanates
- H01G4/1227—Ceramic dielectrics characterised by the ceramic dielectric material based on titanium oxides or titanates based on alkaline earth titanates
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Description
本發明係關於一種介電質陶瓷及積層陶瓷電容器,特別是關於一種適用於薄層大容量型之積層陶瓷電容器之介電質陶瓷及使用該介電質陶瓷所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,有謀求積層陶瓷電容器所具備之介電質陶瓷層之薄層化之方法。但是,伴隨介電質陶瓷層之不斷薄層化,每一層介電質陶瓷層之電場強度變得更高。因此,對於所使用之介電質陶瓷,要求更進一步之可靠性,特別是於負荷試驗中,要求更高之壽命特性。
另一方面,作為構成積層陶瓷電容器之介電質陶瓷層之介電質陶瓷,通常使用BaTiO3
系介電質陶瓷。另外,於BaTiO3
系介電質陶瓷中,為了使可靠性及各種電特性良好,而添加稀土類元素及Mn等元素作為副成分。
例如,於日本專利特開平10-330160號公報(專利文獻1)中,為了謀求絕緣擊穿電壓之提高,而揭示有一種介電質陶瓷,該介電質陶瓷係以ABO3
(A一定含有Ba,進而,有時含有Ca及Sr之至少一種。B一定含有Ti,進而,有時含有Zr、Sc、Y、Gd、Dy、Ho、Er、Yb、Tb、Tm及Lu中之至少1種)為主成分之芯殼構造之介電質陶瓷,其中,Mn、V、Cr、Co、Ni、Fr、Nb、Mo、Ta及W中之至少1種大致均勻地分佈於粒子整體中。另外,於專利文獻1中揭示有一種以Mg為殼成分,該Mg不分佈於芯中而僅分佈於殼部中之實施例。
但是,即便於使用上述專利文獻1中記載之介電質陶瓷之情形時,若進一步推進介電質陶瓷層之薄層化,則於可靠性、特別是負荷試驗中之壽命特性方面亦存在不充分之方面,期望更進一步之改善。
[專利文獻1]日本專利特開平10-330160號公報
因此,本發明之目的在於提供一種即便進行介電質陶瓷層之薄層化,亦能夠實現高可靠性之介電質陶瓷及使用該介電質陶瓷所構成之積層陶瓷電容器。
本發明之介電質陶瓷之特徵在於,主成分為(Ba,R)(Ti,V)O3
系或(Ba,Ca,R)(Ti,V)O3
系(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)。簡單而言,本發明之介電質陶瓷之特徵在於,V及R兩者均勻地存在於主成分粒子內。
本發明之介電質陶瓷中,於(Ba,R)位或(Ba,Ca,R)位整體中,R之含有比較佳為0.01~2莫耳%。
另外,於(Ti,V)位整體中,V之含有比較佳為0.01~1莫耳%。
另外,於(Ba,Ca,R)位整體中,Ca之含有比較佳為0.01~15莫耳%。
另外,本發明亦提供一種積層陶瓷電容器,其具備:電容器主體,其係以積層而成之複數個介電質陶瓷層、與沿介電質陶瓷層間之特定界面所形成之複數個內部電極構成;及複數個外部電極,其形成於電容器主體之外表面上之相互不同的位置,且電性連接於上述內部電極之特定者。
本發明之積層陶瓷電容器之特徵在於,介電質陶瓷層包含上述本發明之介電質陶瓷。
根據本發明之介電質陶瓷,藉由將R與V保持電荷平衡,並且使其分別均勻地固溶於主成分粒子內,而能夠於不使主成分粒子內之絕緣性降低之情況下抑制氧缺陷量之減少或氧缺陷之移動。
因此,若使用本發明之介電質陶瓷構成積層陶瓷電容器,則即便使介電質陶瓷層薄層化,亦可實現高可靠性、特別是於負荷試驗中良好之壽命特性。
本發明之介電質陶瓷中,若於(Ba,R)位或(Ba,Ca,R)位整體中,R之含有比選擇為0.01~2莫耳%,則可使壽命特性更加良好。
另外,於若(Ti,V)位整體中,V之含有比選擇為0.01~1莫耳%,則可使壽命特性更加良好。
另外,若於(Ba,Ca,R)位整體中,Ca之含有比選擇為0.01~15莫耳%,則可使壽命特性更加良好。
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具備電容器主體5,該電容器主體5係以積層而成之複數個介電質陶瓷層2、與沿介電質陶瓷層2間之特定界面所形成之複數個內部電極3及4構成。內部電極3及4例如以Ni為主成分。
於電容器主體5之外表面上之相互不同之位置上形成第1及第2外部電極6及7。外部電極6及7例如以Ag或Cu為主成分。於圖1所示之積層陶瓷電容器1中,第1及第2外部電極6及7形成於電容器主體5之相互對向之各端面上。內部電極3及4有電性連接於第1外部電極6之複數個第1內部電極3與電性連接於第2外部電極7之複數個第2內部電極4,該等第1及第2內部電極3及4從積層方向觀察係交替地配置。
再者,積層陶瓷電容器1可為具備2個外部電極6及7之2端子型電容器,亦可為具備複數個外部電極之多端子型電容器。
於此種積層陶瓷電容器1中,介電質陶瓷層2包含主成分為(Ba,R)(Ti,V)O3
系或(Ba,Ca,R)(Ti,V)O3
系(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)之介電質陶瓷。此處,應注意R及V兩者保持電荷平衡,並且均勻地固溶於主成分粒子內。
如此,藉由使R與V均勻地固溶於主成分粒子內,可於不降低主成分粒子內之絕緣性之情況下抑制氧缺陷量之減少或氧缺陷之移動。因此,若使用該介電質陶瓷構成積層陶瓷電容器1,則即便使介電質陶瓷層2薄層化,亦可實現高可靠性、特別是於負荷試驗中良好之壽命特性。
關於上述R之含有比,若於(Ba,R)位或(Ba,Ca,R)位整體中為0.01~2莫耳%,則可進一步提高壽命特性。
另外,關於V之含有比,若於(Ti,V)位整體中為0.01~1莫耳%,則可進一步提高壽命特性。
另外,若於上述介電質陶瓷中,主成分為(Ba,Ca,R)(Ti,V)O3
系,即,使Ca固溶於Ba位,則與主成分為(Ba,R)(Ti,V)O3
系之情形相比,可獲得更高之可靠性。關於該Ca之含有比,若於(Ba,Ca,R)位整體中為0.01~15莫耳%,則可進一步提高壽命特性。
於製作用於介電質陶瓷之原料時,首先製作(Ba,R)(Ti,V)O3
系或(Ba,Ca,R)(Ti,V)O3
系之主成分粉末。因此,例如可應用將含有主成分之構成元素之氧化物、碳酸化物、氯化物、金屬有機化合物等化合物粉末以特定之比例混合並預燒等之固相合成法。此時,藉由例如調節預燒溫度,而控制獲得之主成分粉末之粒徑。再者,亦可應用水熱合成法、水解法等代替上述固相合成法。
另一方面,視需要準備分別含有作為副成分之例如Mn及Si之氧化物、碳酸化物、氯化物、金屬有機化合物等化合物粉末。而且,藉由以特定之比例將該等副成分粉末與上述主成分粉末混合,而獲得用於介電質陶瓷之原料粉末。
為了製造積層陶瓷電容器1而實施下述步驟:使用如上所得之介電質陶瓷原料粉末製作陶瓷漿液,由陶瓷漿料成形陶瓷生片,藉由將該等複數片陶瓷生片積層而獲得欲成為電容器主體5之未加工積層體,且對該未加工積層體進行煅燒。在煅燒該生積層體之步驟中,煅燒如上所述調配而成之介電質陶瓷原料粉末,獲得包含燒結而成之介電質陶瓷之介電質陶瓷層2。
以下,基於本發明對實施之實驗例進行說明。
[實驗例1]
於實驗例1中,將主成分為(Ba,R)(Ti,V)O3
系之情況與主成分為(Ba,R)TiO3
系及Ba(Ti,V)O3
系之各種情況加以比較。
(A) 陶瓷原料之製作
首先,準備作為微粒之BaCO3
、TiO2
、R2
O3
之Dy2
O3
、及V2
O5
之各粉末作為主成分之起始原料,如表1之「主成分粒內組成」一欄所示,按照於試樣101中成為(Ba0.99
Dy0.01
)TiO3
、於試樣102中成為Ba(Ti0.995
V0.005
)O3
、於試樣103中成為(Ba0.99
Dy0.01
)(Ti0.995
V0.005
)O3
之方式,分別稱量該等粉末,以水作為介質利用球磨機混合8小時。然後,進行蒸發乾燥,於1100℃之溫度下預燒2小時,藉此獲得試樣101~103各自之主成分粉末。
接著,準備作為副成分之MnCO3
及SiO2
之各粉末,相對於上述主成分100莫耳份,以Mn為0.25莫耳份、及Si為1.5莫耳份之方式稱量該等MnCO3
及SiO2
之各粉末,並將其調配於上述主成分粉末中,接著,以水作為介質利用球磨機混合24小時。然後,進行蒸發乾燥,獲得試樣101~103各自之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加入聚乙烯丁醛系黏合劑及乙醇,利用球磨機進行16小時濕式混合,藉此製作陶瓷漿料。
接著,利用唇模方式使該陶瓷漿料成形為片狀,獲得陶瓷生片。
接著,於上述陶瓷生片上網版印刷以Ni為主體之導電性膏,形成欲成為內部電極之導電性膏膜。
接著,以導電性膏膜之拉出側相互不同之方式積層複數片形成有導電性膏膜之陶瓷生片,獲得欲成為電容器主體之生積層體。
接著,將生積層體於N2
氣氛中加熱至300℃之溫度,使黏合劑燃燒後,於氧分壓為10-10
MPa之包含H2
-N2
-H2
O氣體之還原性氣氛中,於1200℃之溫度下進行2小時煅燒,獲得燒結之電容器主體。
接著,於燒結後之電容器主體之兩端面上塗佈含有B2
O3
-Li2
O-SiO2
-BaO系玻璃粉之Cu膏,於N2
氣氛中以800℃之溫度進行燒結,形成與內部電極電性連接之外部電極,獲得作為試樣之積層陶瓷電容器。
如此獲得之積層陶瓷電容器之外形尺寸為:長度為2.0 mm、寬度為1.2 mm、厚度為1.0 mm,介於內部電極間之介電質陶瓷層之厚度為1.0 μm。另外,有效介電質陶瓷層之層數為100層,每一層陶瓷層之內部電極之對向面積為1.4 mm2
。
(C) 特性評價
對獲得之積層陶瓷電容器實施高溫負荷壽命試驗。於高溫負荷壽命試驗中,對100個試樣,於溫度125℃下施加12 V之直流電壓(12 kV/mm之電場強度),將在經過1000小時之時點絕緣電阻值為100 kΩ以下之試樣判定為不良,求出不良個數。其結果示於表1之「高溫負荷壽命試驗不良個數」一欄。
由表1可知,根據主成分粒子之組成為(Ba0.99
Dy0.01
)(Ti0.995
V0.005
)O3
之試樣103,於高溫負荷壽命試驗中不產生不良,與試樣101及102相比,顯示出優異之可靠性。推測起原因在於,在試樣103中,Dy及V兩者均勻地固溶於主成分粒子內。
[實驗例2]
在實驗例2中,與實驗例1中之試樣103之情況同樣,針對使主成分為(Ba,R)(Ti,V)O3
系,並且使V量及R量變化之介電質陶瓷進行評價。
(A) 陶瓷原料之製作
使用Dy作為R,並且作為主成分粉末之組成為(Ba1-x/100
Dyx/100
)(Ti1-y/100
Vy/100
)O3
,以分別具有表2之「x」及「y」一欄所示之值之方式調整作為(Ba,R)位中之R之Dy之含有比x及(Ti,V)位中之V之含有比y,除此之外,利用與實驗例1之情況同樣之要點獲得介電質陶瓷原料粉末。
(B) 積層陶瓷電容器之製作
使用上述介電質陶瓷原料粉末,利用與實驗例1之情況同樣之要點製作各試樣之積層陶瓷電容器。
(C) 特性評價
利用與實驗例1之情況同樣之要點,實施高溫負荷壽命試驗。其結果示於表2之「高溫負荷壽命試驗不良個數」一欄。
由表2可知,在全部之試樣201~210中,顯示出良好之可靠性,但其中,根據主成分粒子中之Dy含有比即「x」為0.01~2之範圍,且V含有比即「y」選擇為0.01~1之範圍之試樣201~204、207及208,於高溫負荷壽命試驗中完全不產生不良,顯示出更良好之可靠性。
相對於此,試樣206之結果為可靠性稍差。推測起原因在於,主成分粒子之Dy含有比「x」超過2,電荷平衡被破壞。
另外,試樣205及209之結果亦為可靠性稍差。推測其原因在於,主成分粒子之V含有比「y」超過1。
另外,試樣210之結果亦為可靠性稍差。推測其原因在於,主成分粒子之Dy含有比「x」超過2,且V含有比「y」亦超過1,主成分粒子內之添加成分Dy及V之分散性產生不均。
由該等可知,若R之含有比即「x」為0.01~2之範圍,且V之含有比即「y」若在0.01~1之範圍,則可獲得高可靠性。
[實驗例3]
於實驗例3中,關於實驗例1中之試樣103之主成分粒子內之組成,將作為R之Dy替換為表3之「R種」一欄所示之元素,除此之外,利用與實驗例1之情況同樣之要點製作各試樣之積層陶瓷電容器,另外,利用同樣之要點實施高溫負荷壽命試驗。再者,於實驗例3中,在高溫負荷壽命試驗中,不僅求出在經過1000小時之時絕緣電阻值成為100 kΩ以下之試樣的不良個數,而且求出在經過2000小時之時絕緣電阻值成為100 kΩ以下之試樣的不良個數。
由表3可知,於試樣301~307之任一個中,均顯示出優異之可靠性。
[實驗例4]
實驗例4對應於實驗例1。在實驗例1中,使主成分為(Ba,R)(Ti,V)O3
系,在實驗例4中,使主成分為(Ba,Ca,R)(Ti,V)O3
系。
(A) 陶瓷原料之製作
首先,準備微粒之BaCO3
、CaCO3
、TiO2
、Gd2
O3
及V2
O5
之各粉末作為主成分之起始原料,如表4之「主成分粒內組成」一欄所示,按照於試樣401中成為(Ba0.98
Ca0.01
Gd0.01
)TiO3
、於試樣402中成為(Ba0.99
Ca0.01
)(Ti0.995
V0.005
)O3
、於試樣403中成為(Ba0.98
Ca0.01
Gd0.01
)(Ti0.995
V0.005
)O3
之方式,分別稱量該等粉末,以水作為介質利用球磨機進行8小時混合。然後,進行蒸發乾燥,於1100℃之溫度下進行2小時預燒,獲得主成分粉末。
接著,準備作為副成分之MnCO3
及SiO2
之各粉末,相對於上述主成分100莫耳份,以Mn成為0.25莫耳份、及Si成為1.5莫耳份之方式秤量該等MnCO3
及SiO2
之各粉末,並將其調配於上述主成分粉末中,接著,以水作為介質利用球磨機進行24小時混合。然後,進行蒸發乾燥,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醇縮丁醛系黏合劑及乙醇,藉由利用球磨機進行16小時濕式混合,藉此製作陶瓷漿料。
然後,實施與實驗例1之情況同樣之步驟,獲得作為試樣之積層陶瓷電容器。
(C) 特性評價
利用與實施例1之情況同樣之要點對獲得之積層陶瓷電容器實施高溫負荷壽命試驗。再者,在實驗例4中,除對經過1000小時之時進行評價外,亦對經過2000小時之時進行評價。其結果示於表4之「高溫負荷壽命試驗不良個數」一欄。
由表4可知,根據主成分粒子之組成為(Ba0.98
Ca0.01
Gd0.01
)(Ti0.995
V0.005
)O3
之試樣403,在高溫負荷壽命試驗中,無論在經過1000小時之時還是在經過2000小時之時,均不產生不良,與試樣401及402相比,顯示出優異之可靠性。推測其原因在於,於試樣403中,Dy及V兩者均勻地固溶於主成分粒子內。
[實驗例5]
於實驗例5中,與實驗例4之情況同樣,對使主成分為(Ba,Ca,R)(Ti,V)O3
系,並且使Ca量、R量及V量變化之介電質陶瓷進行評價。
(A) 陶瓷原料之製作
作為主成分粉末,組成為(Ba1-x-y/100
Cax/100
Gdy/100
)(Ti1-z/100
Vz/100
)O3
,以(Ba,Ca,R)位中之Ca之含有比x及作為R之Gd之含有比y分別具有表5之「x」及「y」一欄所示之值,且(Ti,V)位中之V之含有比z具有表5之「z」一欄所示之值之方式進行調整,除此之外,利用與實驗例4之情況同樣之要點,獲得介電質陶瓷原料粉末。
(B) 積層陶瓷電容器之製作
使用上述介電質陶瓷原料粉末,利用與實驗例4之情況同樣之要點製作各試樣之積層陶瓷電容器。
(C)特性評價
利用與實驗例4之情況同樣之要點,實施高溫負荷壽命試驗。其結果示於表5之「高溫負荷壽命試驗不良個數」一欄。
由表5可知,於全部之試樣501~513中,均顯示出良好之可靠性,但其中,根據Ca之含有比即「x」為0.01~15、作為R之Gd之含有比即「y」為0.01~2、且V之含有比即「z」為0.01~1之範圍之試樣501~505、507、508、510及511,於高溫負荷壽命試驗中,無論是經過1000小時之時還是經過2000小時之時,均不產生不良。
相對於此,根據Ca之含有比即「x」超過15之試樣506、及作為R之Gd含有比即「y」超過2之試樣509、進而Ca之含有比即「x」超過15、作為R之Gd含有比即「y」超過2、且V之含有比即「z」超過1之試樣513,於高溫負荷壽命試驗中,在經過1000小時之時及經過2000小時之時產生微少之不良。
另外,根據V之含有比即「z」超過1之試樣512,於高溫負荷壽命試驗中,在經過1000小時之時不產生不良,在經過2000小時之時產生微小之不良。
由此可知,若Ca之含有比即「x」為0.01~15,R之含有比即「y」為0.01~2,且V之含有比即「z」為0.01~1之範圍,則可獲得更高之可靠性。
[實驗例6]
實驗例6對應於實驗例3。
於實驗例6中,關於實驗例4中之試樣403之主成分粒子內之組成,除將作為R之Gd替換為表6之「R種」一欄所示之元素以外,利用與實驗例4之情況同樣之要點製作各試樣之積層陶瓷電容器,另外,利用同樣之要點實施高溫負荷壽命試驗。
由表6可知,於任一試樣601~607中,均顯示出優異之可靠性。
1...積層陶瓷電容器
2...介電質陶瓷層
3、4...內部電極
5...電容器主體
6、7...外部電極
圖1為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...電容器主體
6、7...外部電極
Claims (2)
- 一種介電質陶瓷,其特徵在於:主成分為(Ba,R)(Ti,V)O3 系,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,其中於(Ba,R)位整體中,R之含有比為0.01~2莫耳%,於(Ti,V)位整體中,V之含有比為0.01~1莫耳%。
- 一種積層陶瓷電容器,其包括:電容器主體,其係以積層而成之複數個介電質陶瓷層、與沿上述介電質陶瓷層間之特定界面所形成之複數個內部電極構成;及複數個外部電極,其形成於上述電容器主體之外表面上之相互不同的位置,且電性連接於上述內部電極之特定者;且上述介電質陶瓷層包含如請求項1之介電質陶瓷。
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CN103563024B (zh) * | 2011-08-02 | 2016-08-24 | 株式会社村田制作所 | 层叠陶瓷电容器 |
TWI471288B (zh) * | 2012-12-28 | 2015-02-01 | Holy Stone Entpr Co Ltd | 積層陶瓷電容用介電陶瓷材料 |
KR20160095383A (ko) * | 2015-02-03 | 2016-08-11 | 삼성전기주식회사 | 유전체 조성물 및 이를 포함하는 적층 세라믹 커패시터 |
CN105236959A (zh) * | 2015-08-25 | 2016-01-13 | 成都顺康三森电子有限责任公司 | 一种低介电损耗、低温度系数的微波电子陶瓷的生产工艺 |
CN105036745A (zh) * | 2015-08-25 | 2015-11-11 | 成都顺康三森电子有限责任公司 | 一种低介电损耗、低温度系数的微波电子陶瓷原料 |
CN107903052A (zh) * | 2017-11-17 | 2018-04-13 | 武汉科技大学 | 一种六钛酸钾晶须多孔陶瓷及其制备方法 |
JP7089402B2 (ja) * | 2018-05-18 | 2022-06-22 | 太陽誘電株式会社 | 積層セラミックコンデンサおよびその製造方法 |
JP7145652B2 (ja) * | 2018-06-01 | 2022-10-03 | 太陽誘電株式会社 | 積層セラミックコンデンサおよびその製造方法 |
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CN102199038A (zh) | 2011-09-28 |
TW201204677A (en) | 2012-02-01 |
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