CN1505071A - 可低温烧结的电介质陶瓷组合物及使用它的多层陶瓷片状电容器 - Google Patents

可低温烧结的电介质陶瓷组合物及使用它的多层陶瓷片状电容器 Download PDF

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CN1505071A
CN1505071A CNA031491006A CN03149100A CN1505071A CN 1505071 A CN1505071 A CN 1505071A CN A031491006 A CNA031491006 A CN A031491006A CN 03149100 A CN03149100 A CN 03149100A CN 1505071 A CN1505071 A CN 1505071A
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dielectric
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金俊熙
许康宪
朴海成
金钟翰
金佑燮
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Samsung Electro Mechanics Co Ltd
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Abstract

可低温烧结的电介质陶瓷组合物和多层陶瓷片状电容器。所述的电介质陶瓷组合物由通式:aBaTiO3-bMgCO3-cY2O3-dCr2O3-eV2O5-f(xZrO2-y(K,Li)2O-zSiO2)(x+y+z=1;0.05≤x≤0.18,0.01≤y≤0.08,以及0.74≤z≤0.93)表示,其中a,b,c,d,e和f为摩尔比;a=100,1.0≤b≤2.0,0.2≤c≤2.0,0.02≤d≤0.3,0.02≤e≤0.3以及0.5≤f<2。所述的多层陶瓷片状电容器使用所述的电介质陶瓷组合物来制备。本发明的电介质组合物可以低温烧结,但介电常数不减小,这使得制造超薄层电介质成为可能。

Description

可低温烧结的电介质陶瓷组合物及使用它的多层陶瓷片状电容器
技术领域
本发明涉及电介质陶瓷组合物,更具体地,涉及可以低温烧结而介电常数不下降的电介质陶瓷组合物,这使得制造超薄层电介质成为可能,并涉及使用该组合物的多层陶瓷片状电容器。
背景技术
随着近来电子设备工业的进展,日益需要开发具有大电容量的小型电子零件。多层陶瓷片状电容器通过交替的电极层和基于高介电常数的陶瓷层形成多层结构。它们作为具有小型和大电容量特征的电子零件被广泛应用。
较为便宜的贱金属如Ni和Ni合金代替昂贵的贵金属如Ag和Pd在多层陶瓷片状电容器中用作内电极。在空气中烧结时,由Ni构成的内电极可以被氧化。因此,必须在还原氛中进行介质层和内电极的共烧。但是,在还原氛中烧结造成介质层被还原,使电阻率低下。因此提出了不可还原的电介质陶瓷材料。
日本专利申请公开2000-311828号公报中公开了一种典型的用于使用Ni作为内电极的电介质陶瓷片状电容器的不可还原的电介质陶瓷组合物。该电介质陶瓷组合物包括BaTiO3:100mol,选自MgO、CaO、BaO、SrO和Cr2O3的至少一种:0.1 to 3mol,(Ba,Ca)xSiO2+x(条件是x=0.8-1.2):2 to 12mol,选自V2O5、MoO3和WO3的至少一种:0.1to 3mol,以及R的氧化物(R为选自Y、Dy、Tb、Gd和Ho的至少一种):0.1 to 10mol。该组合物满足X7R特性(EIA标准),在直流电场中电容量随时间的变化和电容量的下降小。尽管有这些优点,但其烧结温度太高,为1270℃。
如果烧结温度高,则Ni内电极层在比电介质陶瓷层更低的温度下收缩,从而造成两层的界面脱层(interfacial delamination)。另外,由于内电极层间成块(lumping),在内电极间容易产生短路。尤其是为提供电容量大、尺寸小的多层陶瓷片状电容器而将各介质层的厚度减至5μm或5μm以下时,在高烧结温度下内电极间的短路可能更频繁发生。为此,具有Ni内电极的超薄层陶瓷片状电容器用的电介质陶瓷组合物必须在1200℃或1200℃以下的低温烧结。除上面所述的以外,当电介质陶瓷层变薄时,在电介质上施加更高的电压,经常造成介电常数下降、及电容温度特性(下文也称为“TCC”)这样的问题。另外,依赖于DC偏压的电容变化率增大。特别是当介质层的厚度降至3μm或3μm以下时,在内电极间容纳的陶瓷粒子数量更小,这使得难以保证稳定的介电特性。
在美国专利6,243,254号中公开了一种典型的可低温烧结的、薄的多层陶瓷片状电容器。该电容器用的电介质陶瓷组合物含有由通式:(Ba1-xCaxO)mTiO2+αRe2O3+βMgO+γMnO)(Re为选自Y、Gd、Tb、Dy、Ho、Er和Yb的至少一种)表示的主要成分,以及相对于每100重量份主要成分,含有0.2-5.0重量份的第一次要成分Li2O-(Si,Ti)O2-Mn(MO为选自Al2O3和ZrO2的至少一种)或第二次要成分SiO2-TiO2-XO系氧化物(XO为选自BaO、CaO、SrO、MgO、ZnO和MnO的至少一种)。该电介质组合物可以在1250℃或1250℃以下的低温下烧结,并且电容温度特性满足EIA标准规定的X7R特性。但是,当各介质层的厚度降至3μm或3μm以下时,介电常数大幅降至1130-2900的水平。这样,难以制备大电容量的电容器。
发明内容
因此,鉴于上述问题作了本发明。本发明的目的是提供电介质陶瓷组合物,它可低温烧结且介电常数不下降,这使得制造超薄层电介质成为可能;并且它满足X5R特性(EIA标准)。本发明的另一个目的是提供使用该组合物的多层陶瓷片状电容器。
根据本发明的一方面,通过提供由下面的通式表示的电介质陶瓷组合物可以实现上述及其它目的:aBaTiO3-bMgCO3-cY2O3-dCr2O3-eV2O5-f(xZrO2-y(K,Li)2O-zSiO2)(x+y+z=1;0.05≤x≤0.18,0.01≤y≤0.08,以及0.74≤z≤0.93);其中a,b,c,d,e和f为摩尔比;a=100,1.0≤b≤2.0,0.2≤c≤2.0,0.02≤d≤0.3,0.02≤e≤0.3以及0.5≤f<2。
根据本发明的另一方面,提供一种多层陶瓷片状电容器,通过交替层叠含有上述电介质陶瓷组合物的介质层和内电极制备。
在多层陶瓷片状电容器中,优选内电极选自贱金属如Ni和Ni合金。
在多层陶瓷片状电容器中,优选介质层的厚度为5μm或5μm以下,优选2-5μm。
具体实施方式
以下,更详细地说明本发明。
本发明人发现,在玻璃组合物xZrO2-y(K,Li)2O-zSiO2的存在下,aBaTiO3-bMgCO3-cY2O3-dCr2O3-eV2O5可以低温烧结,并具有高介电常数。本发明是基于该发现完成的。本发明的电介质陶瓷组合物可用来提供具有大电容量的多层陶瓷片状电容器,因为当介质层被做成厚度3μm或3μm以下的超薄状并在低温下烧结时它可以提供3000或3000以上的高介电常数,并且满足X5R特性,具有优良的绝缘电阻以及电容量随DC偏压的变化小。
以下说明本发明的电介质陶瓷组合物。如果没有另外指出,所有电介质成分的含量都是基于100摩尔BaTiO3
[MgCO3]
MgCO3起通过控制BaTiO3粒子的生长形成芯-壳结构的作用。即,MgCO3控制添加剂成分向BaTiO3的中心部分扩散,导致在芯-壳结构的中心部分中仅留有BaTiO3作为芯。为此,优选将MgCO3的含量限制在1.0-2.0摩尔范围内。如果MgCO3的含量低于1.0摩尔,由于BaCO3粒子的过度生长,导致介电常数增加但介电损耗因子增大,且电容温度特性变差。相反,如果MgCO3的含量超过2.0摩尔,烧结性变差,加速寿命(accelerated lifetime)缩短。
[Y2O3]
Y2O3有效延长加速寿命,并提供稳定的电容温度特性。因此,Y2O3的优选添加量为0.2-2.0摩尔。如果Y2O3的含量低于0.2摩尔,加速寿命缩短。另一方面,如果其含量超过2.0摩尔,烧结性变差,介电常数降低。
[Cr2O3]
Cr2O3有效改善不可还原性(non-reducibility)。如果Cr2O3的含量低于0.02摩尔,电介质陶瓷组合物转变成半导体,另一方面,如果超过0.3摩尔,绝缘电阻降低。
[V2O5]
V2O5有效改善可靠性。如果V2O5的含量低于0.02摩尔,加速寿命被缩短,另一方面,如果超过0.3摩尔,介电常数和绝缘电阻降低。
[xZrO2-y(K,Li)2O-zSiO2(x+y+z=1;0.05≤x≤0.18,0.01≤y≤0.08,以及0.74≤z≤0.93)]
加入玻璃组合物ZrO2-(K,Li)2O-SiO2作为低温烧结助剂,因此其发挥将烧结温度降至1200℃或1200℃以下的作用。如果玻璃组合物的含量低于0.5摩尔,烧结性变差,电容温度特性落在标准范围之外。相反,如果其含量为2.0摩尔或2.0摩尔以上,介电常数减小并且发生粒子的过度生长,导致在直流电场中电容量显著减少。
在玻璃组合物ZrO2-(K,Li)2O-SiO2中,加入ZrO2以提高介电常数,并且保证高温下电容量的稳定变化。如果ZrO2的含量(x值)低于0.05,不能保证高温下稳定的电容温度特性。如果超过0.18,对改善介电特性几乎没有效果。同时,加入Li2O或K2O以降低玻璃成分的软化温度,导致低温烧结。如果Li2O或K2O的含量(y值)低于0.01,烧结性变差。相反,如果超过0.08,软化温度太低,因此玻璃组合物在低温下成块。结果,玻璃组合物在烧结温度下不能以液相的形式均匀分散。因此,烧结时发生异常的粒子生长。SiO2是玻璃组合物的主要成分,其含量根据其它玻璃成分的含量确定。
最优选将玻璃组合物的粒径限制为0.5μm或0.5μm以下。如果玻璃组合物的粒径超过0.5μm,由于烧结过程中某些熔融玻璃组合物的偏析,导致发生异常的粒子生长。结果,介电特性变差,玻璃组合物可能在烧结体表面上偏析。
优选将BaTiO3的粒径限制为0.4μm或0.4μm以下。在满足X5R特性的电介质组合物中,烧结体的粒径几乎与起始物BaTiO3的粒径相等。因此,当BaTiO3的粒径变小时,介电常数降低。在这一点上,优选增大BaTiO3的粒径。但是,为制作超薄层电介质(厚度约3μm或3μm以下),需要将BaTiO3的粒径限制为0.4μm或0.4μm以下。当介质层变得更薄时,每单位厚度的电场强度增加。因此,如果BaTiO3的粒径超过0.4μm,电容量随DC偏压的变化率过度增加。
以下,说明本发明的多层陶瓷片状电容器。
本发明的多层陶瓷片状电容器通过交替层叠含有上述电介质陶瓷组合物的介质层和内电极来制备。优选将各介质层的厚度限制为5μm或5μm以下,更优选2-5μm,以制备具有大电容量的电容器。贱金属如Ni和Ni合金优选作为内电极材料。外电极由导电金属粉末如Ag、Pd、Ag-Pd、Cu和Cu合金的烧结层构成,或者,由添加有玻璃粉(glassfrit)的导电金属粉末的烧结层构成。可以在其上形成镀层。镀层由Ni、Cu或Ni-Cu合金构成,或可以在其上形成含有锡或焊料的镀层。
根据本发明的多层陶瓷片状电容器的制备方法,首先,通过固相法或湿合成法如水热合成法和醇盐法制备电介质陶瓷组合物的粉末状起始材料。将制备的材料以上述规定的组成比混合。通过加入有机粘合剂将混合的粉末变为浆料。将浆料成形为板状。然后在板的一个面上形成内电极。可使用包括丝网印刷、真空淀积或镀法的任何方法形成内电极。然后,将所需数目具有内电极的板层压,压制后形成层压体。在层压体的两面上形成一对外电极,从而与内电极电连接。最后,如果需要,在外电极上形成镀层,这样就完成了多层陶瓷片状电容器。本发明的电介质陶瓷组合物的烧结在1200℃或1200℃以下,优选在1150-1200℃完成。
以下,通过非限制性实施例更详细地说明本发明。
实施例
在1300-1400℃的温度下称量、混合、溶解烧结助剂ZrO2-(K,Li)2O-SiO2的各成分,迅速在水中淬火并干式研磨,然后使用乙醇进行研磨,从而得到粒径为0.5μm或0.5μm以下的玻璃组合物粉末。
然后,将BaTiO3和添加剂成分混合之前,单独将添加剂成分混合。具体地,将上述玻璃组合物粉末混合物、与MgCO3、Y2O3、Cr2O3和V2O5粉末进行称量并湿式混合24小时,然后在100℃干燥3小时或3小时以上。混合的添加剂成分的平均粒径为0.3-0.4μm。优选混合的添加剂成分的最大粒径为3μm。
接下来,将BaTiO3和先前混合的添加剂成分混合、分散。具体地,将粒径为0.4μm的BaTiO3与先前混合的添加剂成分在溶剂和分散剂的存在下混合、分散3-4小时。
加入粘合剂制成浆料,然后将浆料成形为板状。成形为板状的操作在过滤和稳定浆料后进行。用口模式涂布机将浆料转变为厚度2.8μm的板。在转变的板上印刷尺寸2012(2.0mm×1.2mm)的内电极图案,然后将20层印刷有图案的板一个接一个地层压。在85℃、1000kg/cm2的压力下,用CIP(冷等静压机)将得到的层压体切割15分钟,从而形成片,将形成的片用作评价介电特性的试样。
在250-300℃的空气中热处理各个片试样以除去粘合剂。然后,在管式炉中,在适当的烧结温度和气氛下进行烧结。烧结时的氧气分压设定为10-11atm,并继续在1180℃进行烧结2小时。In-Ga用作外电极。
评价如上制作的片试样的介电特性。电容量和介电损耗在1KHz、1Vrms下,使用电容计(Agilent,4284A)测定。使用下式:C=ε0·εr×S/d×n(C:电容量,ε0:真空介电常数;εr:介电常数;S:电极重叠面积;d:介质层厚度;n:介质层数)计算介电常数。通过在6.3V的DC偏压下,使用4284A计算1KHz、1Vrms的电容量变化率来评价DC偏压特性。使用高阻计(Agilent,4339B)测得的绝缘电阻,由下式:R×C=ρ·ε0·εr(R:绝缘电阻;C:电容量;ρ:电阻率;ε0:真空介电常数;εr:介电常数)计算电阻率。在-55℃-85℃(X5R特性)的温度范围中,使用4220A试验室(test chamber)评价电容温度特性(TCC)。通过用SEM(扫描电镜)观察片的表面破裂评价烧结性。
表1
                       电介质组合物(基于100摩尔 BaTiO3)
          bMgCO3   cY2O3    dCr2O3  eV2O5    f(xZrO2-y(Li,K)2O-zSiO2)          烧结温度
试样
          1.0≤b    0.2≤c     0.02≤d    0.02≤e  0.5≤f  0.05≤x    0.01≤y        0.74≤z    (℃)
          ≤2.0     ≤2.0      ≤0.3      ≤0.3    <2.0   ≤0.18     ≤0.08         ≤0.93
Inv.1      1.3       0.6        0.2        0.1     0.7     0.07       0.02(Li2O)    0.91       1180
Comp.2     1.3       0.6        0.2        0.1     0.7     0.03       0.02(Li2O)    0.95       1180
Inv.3      1.3       0.6        0.2        0.1     0.7     0.1        0.04(Li2O)    0.86       1180
Comp.4     1.3       0.6        0.2        0.1     0.7     0.1        0.15(K2O)     0.75       1180
Comp.5     1.4       0.6        0.2        0.1     0.4     0.07       0.02(Li2O)    0.91       1180
Comp.6     1.4       0.6        0.2        0.1     0.4     0.1        0.04(Li2O)    0.86       1180
Comp.7     1.4       0.2        0.1        0.1     2.0     0.07       0.02(Li2O)    0.91       1180
Comp.8     1.5       0.3        0.1        0.1     2.0     0.1        0.04(K2O)     0.86       1180
Inv.9      1.5       0.9        0.08       0.03    0.7     0.07       0.02(Li2O)    0.91       1180
Inv.10     1.6       0.9        0.1        0.1     0.9     0.1        0.04(Li2O)    0.86       1180
Inv.11     1.6       0.9        0.08       0.03    0.9     0.1        0.04(Li2O)    0.86       1180
Comp.12    1.3       2.5        0.1        0.1     0.7     0.07       0.02(Li2O)    0.91       1180
Comp.13    1.3       2.5        0.1        0.1     0.9     0.07       0.02(Li2O)    0.91       1180
Comp.14    1.4       0.3        0          0.1     0.7     0.1        0.04(Li2O)    0.86       1180
Comp.15    1.4       0.3        0.1        0.4     0.7     0.1        0.04(Li2O)    0.86       1180
Inv.16     1.4       1.5        0.2        0.1     0.7     0.1        0.04(K2O)     0.86       1180
                                    Inv.:本发明试样    Comp.:比较试样
表2
                    介电                TCC(%)               电阻率
           介电
试样                损耗                                      ×1011   电容量减小率(%)    烧结性  评价
           常数               -55℃    0℃    45℃    85℃
                    (%)                                     (Ω·cm)
Inv.1      3700     4.0       -5.0     0.0    0.2    -8.0       20          -40              好      好
Comp.2     3450     3.4        2.0     2.0   -5.0    -17.0      22          -42              好      D
Inv.3      3720     3.8       -6.0    -1.0    1.2    -10.0      23          -39              好      好
Comp.4     4200     7.0       -16.0   -4.1    1.2    -16.5      18          -64              A       D,E
Comp.5     3000     3.0       -4.0     0.2    1.2    -7.0       1.2         -40              B       F
Comp.6     2800     2.9       -4.2     0.3    1.5    -6.8       2.1         -42              B       F
Comp.7     4200     5.6       -15.5   -6.0    1.3    -15.2      25          -65              A       D,E,G
Comp.8     4300     6.3       -16.0   -5.2    2.0    -16.2      28          -67              A       D,E,G
Inv.9      3450     3.5       -7.0    -1.7    1.2    -12.0      30          -37              好      好
Inv.10     3500     3.7       -6.5    -1.0    1.0    -10.0      20          -38              好      好
Inv.11     3600     3.8       -8.0     0.2   -0.2    -11.0      40          -40              好      好
Comp.12    3000     2.7       -5.0    -1.8    0.1    -5.0       1.2         -35              B       F
Comp.13    3100     2.8       -6.0    -2.0   -0.1    -6.0       1.5         -37              B       F
Comp.14                                                  转变成半导体
Comp.15    3000     2.7       -7.0    -2.0   -0.2    -7.0       0.1         -38              C       H
Inv.16     3200     3.0       -4.0     0.0    1.0    -3.0       20          -35              好      好
                        Inv.:本发明试样,Comp.:比较试样,A:粒子生长,B:未烧结,
                            C:电阻率减小,D:TCC不良,E:DC偏压特性不良,
                             F:烧结性不良,G:介电损耗,H:绝缘电阻不良
如表1和表2所示,比较试样2的片,其中(xZrO2-y(Li,K)2O-zSiO2)的含量为0.7mol,表现出良好的烧结性。但是,起确保高温的稳定TCC作用的ZrO2含量太小,导致高温(85℃)的电容量变化大。
比较试样4的片表现出异常的粒子生长。这是因为过量K2O降低了玻璃组合物的软化温度,导致玻璃组合物在低温下成块。结果,在烧结温度下,该玻璃组合物不能以液相的形式均匀分散,从而在烧结时可能发生异常的粒子生长。这样的异常的粒子生长导致高介电常数,但介电损耗增加,并且DC偏压特性和电容温度特性变差。
对于比较试样5和6的片而言,玻璃组合物的含量太小,因此不发生烧结。另外,介电常数和绝缘电阻减小。
对于比较试样7和8的片而言,加入了过量玻璃组合物,因此发生了过度的粒子生长。结果,介电常数增加,但介电损耗增大,并且TCC和DC偏压特性变差。
比较试样12和13的片具有令人满意的玻璃组合物,但由于过量Y2O3而使烧结性变差。
比较试样14的组合物,其中没加Cr2O3,由于不可还原性差而转变成半导体。
比较试样15的片,其中加有过量V2O5,表现出低介电常数和差的绝缘电阻。因此,该片试样缺乏工业实用性。
但是,本发明试样1、3、9、10、11和16的片表现出良好的介电特性。
从上面的说明明显可以看出,本发明的电介质陶瓷组合物可以以超薄层的形式在1200℃或1200℃以下的低温下与内电极共烧。结果,在内电极间不产生短路。另外,贱金属如Ni或Ni合金可以用作内电极。特别是由于本发明的超薄介质层可以提供高介电常数,因此本发明的电介质陶瓷组合物可以用于制备可靠性高、电容量大的多层陶瓷片状电容器。
尽管公开了本发明的优选实施方案以说明本发明,但本领域的普通技术人员将理解,在不偏离附带的权利要求书中公开的范围和精神的情况下,可以进行多种改进、添加和替代。

Claims (6)

1.由下式表示的可低温烧结的电介质陶瓷组合物:
aBaTiO3-bMgCO3-cY2O3-dCr2O3-eV2O5-f(xZrO2-y(K,Li)2O-zSiO2)(x+y+z=1;0.05≤x≤0.18,0.01≤y≤0.08,以及0.74≤z≤0.93);其中a,b,c,d,e和f为摩尔比;a=100,1.0≤b≤2.0,0.2≤c≤2.0,0.02≤d≤0.3,0.02≤e≤0.3以及0.5≤f<2。
2.如权利要求1所述的组合物,其中BaTiO3的平均粒径为0.4μm或0.4μm以下。
3.如权利要求1所述的组合物,其中xZrO2-y(K,Li)2O-zSiO2的平均粒径为0.5μm或0.5μm以下。
4.多层陶瓷片状电容器,通过交替层叠含有如权利要求1所述的电介质陶瓷组合物的介质层和内电极来制备。
5.如权利要求4所述的多层陶瓷片状电容器,其中内电极选自Ni和Ni合金。
6.如权利要求4所述的多层陶瓷片状电容器,其中介质层的厚度为2-5μm。
CNB031491006A 2002-12-03 2003-06-26 可低温烧结的电介质陶瓷组合物及使用它的多层陶瓷片状电容器 Expired - Fee Related CN1327462C (zh)

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