CN1576260A - 介电陶瓷组合物和陶瓷电子元件 - Google Patents

介电陶瓷组合物和陶瓷电子元件 Download PDF

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CN1576260A
CN1576260A CNA200410071661XA CN200410071661A CN1576260A CN 1576260 A CN1576260 A CN 1576260A CN A200410071661X A CNA200410071661X A CN A200410071661XA CN 200410071661 A CN200410071661 A CN 200410071661A CN 1576260 A CN1576260 A CN 1576260A
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dielectric ceramic
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伴野晃一
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Abstract

一种介电陶瓷组合物包含100重量份由a[(SrbCa1－b)TiO3]－(1－a)[Bi2O3·nTiO2]表示的主要组分，其中a和b为摩尔量，和n为TiO2与Bi2O3的摩尔比；w重量份的MgTiO3；x重量份的SiO2；y重量份的MnOm (等量的MnCO3)；和z重量份的LnOk，其中m为1至2；Ln为镧，铈，镨，钕，钐，铕，钆，镝，钬和铒中的至少一种；且k为1.5至2，以便LnOk为电中性的，其中a，b，n，w，x，y和z满足关系式：0.90≤a≤0.95，0.90≤b≤0.95，1.8≤n≤3.0，5.0≤w≤10.0，0.1≤x≤1.0，0.1≤y≤0.3，和1.0≤z≤5.0。

Description

介电陶瓷组合物和陶瓷电子元件
技术领域
本发明涉及介电陶瓷组合物，并且具体而言，涉及一种显示高介电常数的介电陶瓷组合物。它还涉及一种用该介电陶瓷组合物制成的陶瓷电子元件。
背景技术
BaTiO3陶瓷被广泛用作高介电常数的陶瓷组合物。然而，BaTiO3陶瓷在高频率，即1MHz或以上时显示低Q值。为了克服这个问题，日本未审查专利申请公开 62-295304中教导了一种SrTiO3-MgTiO3-CaTiO3-Bi2O3-TiO2-CuO-MnO-CeO2陶瓷组合物。尽管这种组合物具有高介电常数ε和在1MHz或以上的频率时高Q，且介电常数相对于温度变化显示微小变化，但体积电阻率仅为1012至1013欧姆·厘米，其不足够高。
发明内容
发明概述
本发明的一个目的提供具有高介电常数ε和在1MHz或以上频率时Q值至少约为1,000的介电陶瓷组合物，其介电常数相对于温度变化经受微小的变化且显示高体积电阻率。本发明的另一个目的是提供一种用该介电陶瓷组合物制成的陶瓷电子元件。
本发明的第一方面是提供一种介电陶瓷组合物，该组合物包含100重量份的由通式a[(SrbCa1-b)TiO3]-(l-a)[Bi2O3·nTiO2]表示的主要组分，其中a和b为各自的摩尔量和n为TiO2与Bi2O3的摩尔比；w重量份的MgTiO3；x重量份的SiO2；y重量份的MnOm(等量的MnCO3)；和z重量份的LnOk，其中m为1至2；Ln为镧，铈，镨，钕，钐，铕，钆，镝，钬和铒中的至少一种；且k为1.5至2，以便LnOk成为电中性的，且其中a，b，n，w，x，y和z满足以下条件：
0.90≤a≤0.95，
0.90≤b≤0.95，
1.8≤n≤3.0，
5.0≤w≤10.0，
0.1≤x≤1.0，
0.1≤y≤0.3，和
1.0≤z≤5.0。
本发明的第二个方面提供一种包含由上述描述的介电陶瓷组合物组成的陶瓷烧结压块的陶瓷电子元件；和在陶瓷烧结压块的表面上形成的电极。
附图说明
图1为一个单电容，即用根据本发明的一个实施方案介电陶瓷组合物制成的陶瓷电子元件的部分剖面正视图。
优选实施方案描述
现在将详细描述本发明的优选实施方案。图1为一个单电容，即根据本发明的一个实施方案的陶瓷电子元件的部分剖面正视图。这个单电容是用本发明的介电陶瓷组合物制成的。
单电容包括由本发明的介电陶瓷组合物组成的烧结压块1，在烧结压块1的两面形成的电极2，通过焊料3与电极2电连接的引线4a和4b，和覆盖烧结压块1的树脂外壳5。
在这个实施方案中，介电陶瓷组合物包含由通式a[(SrbCa1-b)TiO3]-(l-a)[Bi2O3·nTiO2]表示的主要组分。介电陶瓷组合物还包含：相对于100重量份的主要组分，w重量份的MgTiO3；x重量份的SiO2；y重量份的MnOm(MnCO3当量)和z重量份的LnOk。在通式中，a和b为各自的摩尔量；和n为TiO2与Bi2O3的摩尔比；m为1至2；Ln为镧，铈，镨，钕，钐，铕，钆，镝，钬和铒中的至少一种；且k为1.5至2，以便LnOk成为电中性的。
具体而言，氧的化合价为-2，镧，镨，钕，钐，铕，钆，镝，钬和铒的化合价为+3，和铈的化合价为+4。因此，当Ln为选自+3化合价的元素中的至少一种时，k为1.5。当Ln为+4化合价的元素时，k为2。当Ln包括+3化合价和+4化合价的两种元素时，根据这些元素的比例确定k。
这样制备组合物，以便a，b，n，w，x，y和z满足以下条件：
0.90≤a≤0.95，
0.90≤b≤0.95，
1.8≤n≤3.0，
5.0≤w≤10.0，
0.1≤x≤1.0，
0.1≤y≤0.3，和
1.0≤z≤5.0。
用这种介电陶瓷组合物制成的电容器可以显示高介电常数，即介电常数ε至少为500，在1MHz或以上频率时Q值至少约为1,000，温度系数为-2,000ppm/℃或以下，和体积电阻率为1014欧姆·厘米或以上。
现在将描述制备单电容的方法。
首先，制备介电陶瓷组合物。具体而言，按照上面所述条件称取SrCO3，CaCO3，Bi2O3，TiO2，MgTiO3，SiO2，MnCO3和LnOk并混合。将混合物和研磨剂例如氧化锆放置罐中，并通过湿式混合预定长的时间将混合物磨碎。通过蒸发作用干燥磨碎的混合物，放置氧化锆外壳中，并在约900℃至1,000℃煅烧约2小时。然后，将煅烧过的混合物和粘合剂例如聚乙烯醇，放置罐中并湿式混合预定长的时间。通过脱水作用干燥所得到的混合物，分级，并压制形成为预定的圆盘形的压坯。将压坯在约1,180℃至1,280℃烘焙2小时以制备烧结压块1。
将主要由银等组成的导电膏涂布烧结压块1的两面，并烘焙形成电极2。通过焊料3将引线4a和4b与电极2连接。随后，通过树脂模塑形成外壳5，以制备该电容器。
根据这种方法，可以很容易制造这种单电容，所述单电容具有高介电常数ε和在1MHz或以上的频率时至少约为1,000的Q值，其介电常数相对于温度变化经受微小的变化，且显示高体积电阻率。
本发明不限制于以上所描述的实施方案。例如，介电陶瓷组合物的原料可以是钛酸盐化合物，例如SrTiO3或CaTiO3，而不是TiO2和碳酸盐，例如SrCO3或CaCO3。
介电陶瓷组合物可以用于制造其它的陶瓷电子元件，例如微电容器和单片陶瓷电容器。所得到的元件也将显示高介电常数，高Q值，优越的温度特性和高体积电阻率。
具体实施方式
实施例
准备SrCO3，CaCO3，Bi2O3，TiO2，MgTiO3，SiO2，MnCO3，CeO2，La2O3，Pr2O3，Nd2O3，Sm2O3，Eu2O3，Gd2O3，Dy2O3，Ho2O3，Er2O3，Yb2O3和CuO作为主要和辅助组分的原料。
根据表1分别称重原料并混合以制备样品混合物。如表2所示，样品41至43中包含预定量的CuO。将每一种混合物放置于含有氧化锆球的聚乙烯罐中，并通过湿式混合16小时进行磨碎。通过蒸发作用干燥所得到的磨碎的混合物，将其放置氧化锆外壳中，并在950℃煅烧2小时。
                                              表1
样品号              主要组分                        辅助组分
a b n w x y Ln z
        *1       0.89       0.95        2.0          9.5        0.2        0.2 Ce        3.0
         2       0.92       0.95        2.0          9.5        0.2        0.2 Ce        3.0
        *3       0.96       0.95        2.0          9.5        0.2        0.2 Ce        3.0
        *4       0.91       0.88        2.0          9.5        0.4        0.2 Ce        3.0
         5       0.93       0.90        2.0          9.5        0.3        0.2 Ce        3.0
         6       0.92       0.92        2.0          9.5        0.3        0.2 Ce        1.0
         7       0.92       0.95        3.0          8.0        0.3        0.2 Ce        3.0
        *8       0.94       0.98        2.0          9.5        0.3        0.2 Ce        4.0
        *9       0.92       0.95        1.5          6.0        0.3        0.2 Ce        3.0
        10       0.92       0.90        1.8          9.5        0.3        0.1 Ce        3.0
        11       0.95       0.95        2.0          7.0        0.3        0.2 Ce        2.0
        12       0.92       0.92        2.5         10.0        0.5        0.3 Ce        3.0
        13       0.92       0.95        3.0          5.0        0.3        0.1 Ce        3.0
       *14       0.92       0.94        3.2          9.5        0.1        0.2 Ce        3.0
       *15       0.92       0.95        2.5          4.5        0.3        0.2 Ce        2.0
        16       0.92       0.93        2.0          8.0        0.3        0.2 Ce        5.0
       *17       0.94       0.95        2.0         10.5        0.3        0.2 Ce        4.0
       *18       0.92       0.92        2.0         12.0        0.3        0.1 Ce        3.0
       *19       0.92       0.95        3.0          7.0        0.0        0.2 Ce        3.0
        20       0.92       0.95        3.0          8.0        0.1        0.2 Ce        3.0
       *21       0.93       0.95        2.0          9.0        1.1        0.2 Ce        3.0
       *22       0.92       0.93        2.0          9.5        1.5        0.2 Ce        1.0
       *23       0.91       0.95        2.0          9.5        0.3        0.0 Ce        3.0
        24       0.91       0.95        2.0          9.5        0.3        0.1 Ce        2.0
       *25       0.92       0.95        3.0          8.0        0.3        0.4 Ce        3.0
       *26       0.92       0.94        2.0          9.5        0.2        0.5 Ce        3.0
       *27       0.94       0.95        2.0          6.0        0.3        0.2 Ce        0.0
        28       0.92       0.95        2.5          7.0        0.3        0.2 Ce        2.0
       *29       0.92       0.93        2.0          9.5        0.4        0.2 Ce        6.0
       *30       0.92       0.95        3.0          9.5        0.1        0.2 Ce        7.0
        31       0.92       0.95        2.5          7.0        0.3        0.2 La        2.0
        32       0.92       0.95        2.5          7.0        0.3        0.2 Pr        2.0
        33       0.92       0.95        2.5          7.0        0.3        0.2 Nd        2.0
        34       0.92       0.95        2.5          7.0        0.3        0.2 Sm        2.0
        35       0.92       0.95        2.5          7.0        0.3        0.2 Eu        2.0
        36       0.92       0.95        2.5          7.0        0.3        0.2 Gd        2.0
        37       0.92       0.95        2.5          7.0        0.3        0.2 Dy        2.0
        38       0.92       0.95        2.5          7.0        0.3        0.2 Ho        2.0
        39       0.92       0.95        2.5          7.0        0.3        0.2 Er        2.0
       *40       0.92       0.95        2.5          7.0        0.3        0.2 Yb        2.0
                                                      表2
  样品号             主要组分                             辅助组分
a b n w x y Ln z CuO
       *41       0.92     0.95        2.0        9.5        0.2        0.2 Ce        3.0        0.5
       *42       0.92     0.92        2.0        9.5        0.3        0.2 Ce        3.0        0.3
       *43       0.92     0.95        3.0          8        0.1        0.2 Ce        3.0        0.8
接着，将煅烧过的混合物和聚乙烯醇粘合剂混合，并在聚乙烯罐中湿式混合16小时。通过脱水作用干燥所得到的混合物，分级，并压制成直径为12mm和厚度为1.2mm的圆盘形压坯。将压坯在1,220℃烘焙2小时以制备陶瓷压块。在陶瓷压块的两面通过在800℃烘焙向其涂布的膏料来形成电极，以制备电容器样品。
根据以下的条件和方法确定每一种样品的特性：
介电常数：1MHz，1Vrms，20℃；
Q值：1MHz，1Vrms，在20℃介电损失的倒数；和
温度系数：基于+20℃的介电常数，介电常数在-25℃至85℃的最大变化率。
结果显示于表3和表4。
                               表3
样品号 介电常数ε Q值 温度系数 体积电阻率ρ
    [ppm/℃]    [欧姆·厘米]
          *1          650          847            -1750          4.5×1014
           2          544         1140            -1990          3.8×1014
          *3          435         2540            -2330          8.7×1014
          *4          568          875            -1540          5.2×1014
           5          574         1050            -1760          1.4×1014
           6          532         1210            -1790          2.5×1014
           7          572         1080            -1960          3.5×1014
          *8          578         1260            -2080          7.2×1014
          *9          486         1450            -1990          3.6×1014
          10          514         1380            -1880          5.2×1014
          11          524         1250            -1850          4.8×1014
          12          536         1150            -1800          2.8×1014
          13          558         1030            -1710          7.5×1014
         *14          565          935            -1660          8.9×1014
         *15          542         3520            -2160          4.2×1014
          16          564         1450            -1990          2.8×1014
         *17          535          761            -1850          5.6×1014
         *18          514          518            -1760          4.5×1014
         *19          576         1060            -2070          8.5×1014
          20          584         1040            -1850          4.2×1014
         *21          543          985            -1750          3.8×1014
         *22          557          854            -1670          8.2×1014
         *23          587         1060            -2110          6.5×1014
          24          542         1100            -1950          5.4×1014
         *25          486         1120            -1870          2.6×1014
         *26          452         1150            -1850          7.8×1014
         *27          752          587            -2050          2.5×1014
          28          587         1060            -1850          5.8×1014
         *29          485         1330            -1680          7.1×1014
         *30          389         1560            -1460          3.6×1014
          31          602         1420            -1480          4.7×1014
          32          584         1510            -1450          2.5×1014
          33          578         1520            -1470          7.8×1014
          34          572         1510            -1430          2.8×1014
          35          564         1570            -1420          3.6×1014
          36          550         1530            -1430          4.8×1014
          37          538         1570            -1410          8.6×1014
          38          542         1540            -1430          1.5×1014
          39          515         1550            -1440          5.6×1014
         *40          495         1520            -1430          4.8×1014
                                  表4
样品号 介电常数ε Q值 温度系数 体积电阻率ρ
        [ppm/℃]     [欧姆·厘米]
         *41        538       1250            -1980        5.2×1013
         *42        557       1100            -1840        4.2×1013
         *43        565       1180            -1940        4.8×1013
在表1至4中，加星号的样品不在本发明范围之内，并且没有星号的样品在本发明范围之内。具体而言，表2和4所示且包含CuO的样品不在本发明范围内。从表1至4清楚地看出，基于以下原因，限制了本发明的组合物：
(1)在Bi2O3含量1-a超出0.1时，Q值变得小于约1,000(样品1)。在Bi2O3含量1-a小于0.05时，介电常数变得小于500且温度系数变得小于-2,000ppm/℃(样品3)。
(2)在SrTiO3含量b小于0.9时，Q值变得小于约1,000(样品4)。在SrTiO3含量b超出0.95时，温度系数变得小于-2,000ppm/℃(样品8)。
(3)当TiO2与Bi2O3的摩尔比n小于1.8时，介电常数变得小于500(样品9)。当n超过3时，Q值变得小于约1,000(样品14)。
(4)在MgTiO3含量w小于5时，温度系数变得低于-2,000ppm/℃(样品15)。在w超过10时，Q值变得小于约1,000(样品17和18)。
(5)在SiO2含量x小于0.1时，温度系数变得低于-2,000ppm/℃(样品19)。在x超过1.0时，Q值变得小于约1,000(样品21和22)。
(6)当MnOm含量y(m＝1至2，等量的MnCO3)小于0.1时，温度系数变得低于-2,000ppm/℃(样品23)。当y超过0.3时，介电常数变得小于500(样品25和26)。
(7)在LnOk含量z小于1.0时，Q值变得小于约1,000，且温度系数变得低于-2,000ppm/℃(样品27)。在z超过5.0时，介电常数变得小于500(样品29和30)。
(8)当Ln为不同于上面所述的元素时，介电常数变得小于500(样品40)。
(9)含有CuO的样品的体积电阻率低于1014欧姆·厘米(样品41至43)。

Claims (12)

1.介电陶瓷组合物，其包含：
100重量份的由通式a[(SrbCa1-b)TiO3]-(1-a)[Bi2O3·nTiO2]表示的主要组分，其中a和b为各自的摩尔量，和n为TiO2与Bi2O3的摩尔比；
w重量份的MgTiO3；
x重量份的SiO2；
y重量份的MnOm(计算出作为等量的MnCO3)；和
z重量份的LnOk，
其中m为1至2；Ln为镧，铈，镨，钕，钐，铕，钆，镝，钬和铒中的至少一种；且k为1.5至2，以便LnOk为电中性的，
其中a，b，n，w，x，y和z满足以下条件：
0.90≤a≤0.95，
0.90≤b≤0.95，
1.8≤n≤3.0，
5.0≤w≤10.0，
0.1≤x≤1.0，
0.1≤y≤0.3，和
1.0≤z≤5.0。
2.根据权利要求1所述的介电陶瓷组合物，其中
0.91≤a≤0.95，
0.92≤b≤0.95，
1.8≤n≤2.5，
7.0≤w≤9.5，
0.2≤x≤0.5，和
2.0≤z≤3.0。
3.根据权利要求2所述的介电陶瓷组合物，其中所述的Ln为铈。
4.根据权利要求2所述的介电陶瓷组合物，其中所述的组合物不包含Cu。
5.根据权利要求2所述的介电陶瓷组合物，其中0.92≤a≤0.95。
6.根据权利要求1所述的介电陶瓷组合物，其中所述的Ln为铈。
7.一种陶瓷电子元件，其包括；
包含权利要求6所述的介电陶瓷组合物的陶瓷烧结压块；和
在陶瓷烧结压块表面上的电极。
8.陶瓷电子元件包括；
包含权利要求5所述的介电陶瓷组合物的陶瓷烧结压块；和
在陶瓷烧结压块表面上的电极。
9.陶瓷电子元件包括；
包含权利要求4所述的介电陶瓷组合物的陶瓷烧结压块；和
在陶瓷烧结压块表面上的电极。
10.陶瓷电子元件包括；
包含权利要求3所述的介电陶瓷组合物的陶瓷烧结压块；和
在陶瓷烧结压块表面上的电极。
11.陶瓷电子元件包括；
包含权利要求2所述的介电陶瓷组合物的陶瓷烧结压块；和
在陶瓷烧结压块表面上的电极。
12.陶瓷电子元件包括；
包含权利要求1所述的介电陶瓷组合物的陶瓷烧结压块；和
在陶瓷烧结压块表面上的电极。
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