CN102300832A - 可变电阻陶瓷和含该可变电阻陶瓷的多层构件以及该可变电阻陶瓷的制备方法 - Google Patents

可变电阻陶瓷和含该可变电阻陶瓷的多层构件以及该可变电阻陶瓷的制备方法 Download PDF

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CN102300832A
CN102300832A CN2010800060182A CN201080006018A CN102300832A CN 102300832 A CN102300832 A CN 102300832A CN 2010800060182 A CN2010800060182 A CN 2010800060182A CN 201080006018 A CN201080006018 A CN 201080006018A CN 102300832 A CN102300832 A CN 102300832A
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M.皮伯
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TDK Electronics AG
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Abstract

本发明涉及一种可变电阻陶瓷，其包含下列材料：Zn作为主组分，含量达0.1－3原子%的Pr和含量达0.1－5原子%的选自Y、Ho、Er、Yb、Lu的金属M。

Description

可变电阻陶瓷和含该可变电阻陶瓷的多层构件以及该可变电阻陶瓷的制备方法
本发明涉及一种权利要求1的可变电阻陶瓷。
可变电阻陶瓷的普遍性问题是达到低介电常数(εr)。同时应确保在高电流范围(ESD, 8/20)中足够高的开关强度下的高非线性和低漏电流。
该目的是通过权利要求1的可变电阻陶瓷以及含该可变电阻陶瓷的多层构件和该可变电阻陶瓷的制备方法实现的。该可变电阻陶瓷的其它实施方案列于其它权利要求。
可变电阻是与电压有关的电阻，并可用作过电压保护。
本发明的一个实施方案涉及一种可变电阻陶瓷，其包含下列材料：
-  Zn作为主组分，
-  Pr含量达0.1－3原子%，
-  选自Y、Ho、Er、Yb、Lu的金属M，其含量达0.1－5原子%。
在一种实施方案中，M是Y或Lu。
在一种实施方案中，Co的含量为0.1－10原子%，其中该Co优选以Co2+存在。
在一种实施方案中，Ca的含量为0.001－5原子%，其中该Ca优选以Ca2+存在。
在一种实施方案中，Si的含量为0.001－0.5原子%，其中该Si优选以Si4+存在。
在一种实施方案中，Al的含量为0.001－0.1原子%，其中该Al优选以Al3+存在。
在一种实施方案中，Cr的含量为0.001－5原子%，其中该Cr优选以Cr3+存在。
在一种实施方案中，B的含量为0.001－5原子%，其中该B优选以B3+存在。
对于数字信号的高传输速率，需要具有高的ESD耐用性和冲击电流稳定性和低电容的多层可变电阻。该低电容是必需的，以尽可能小地影响待传输的信号。
可变电阻的电容由下式表示：
C = ε0εr A/d，  (1)
其中，C为电容，ε0为真空的介电常数，εr为相对介电常数，A为两电极之间的面积，d为电极之间的层厚。
该晶间材料的有效介电常数εeff 按Levinson等人(J. Appl. Phys. Vol. 46； No. 3；1975)通以下式表示：
C = εeffε0 [A / (z*d)]      (2)
其中C为电容，ε0为真空的介电常数，z为两电极之间的晶粒-晶粒接触数目，A为电极之间的面积，d为晶粒-晶粒接触的阻挡层厚。
降低多层可变电阻的电容(式(1))的常用方法是通过减小面积A和增大层厚d。但这与多层原理是相反的，因为面积A的减小导致最大的能量可接受性下降，并由此也导致对ESD脉冲而言的冲击电流稳定性以及耐用性降低。
在一种实施方案中，该可变电阻陶瓷包含超出氧化钴和氧化镨的具有低碱性(小的离子半径)的金属M的盐或氧化物的添加剂，如Y3+或Lu3+ (rk 3+=93 pm)。
由此达到该阻挡层的较小的可极化性和阻挡层特性(阻挡层高度和耗尽区的宽度)的控制，以及得到具有每个晶粒-晶粒接触的低电容和同时具有高的非线性和ESD稳定性的可变电阻陶瓷。
通过降低每个晶粒-晶粒接触的电容，在电极之间的相同面积和由此同样好的ESD耐用性和冲击电流稳定性的情况下可得到具有低电容可变电阻构件。
所述优点的细节在实施例中描述。
在一种实施方案中，其阳离子具有较小离子半径(如Y3+，Lu3+)的金属M的氧化物或盐溶于可变电阻陶瓷中，以致该可变电阻陶瓷每个晶粒-晶粒接触具有低电容。
在一个实施例中，在ZnO中加入镨(0.1－3原子%)以及钴(0.1－10原子%)的氧化物作为掺杂物，并且此外还以氧化物形式加入钙(0.001－5原子%)、硅(0.001－0.5原子%)、铝(0.001－0.01原子%)、铬(0.001－5原子%)，以及为在烧结过程中控制结构形态而以化合物形式加入硼(0.001－5原子%)，和以氧化物形式加入钇(0.1－5原子%)。
图1示出多层可变电阻的制备过程流程示意图，其包括下列步骤：A1称重、A2预研磨、A3干燥、A4筛分、A5煅烧、A6后研磨、A7干燥、A8筛分、B1形成浆料、B2坯膜、C1印制导电膏、C2叠置、C3剪切、D1脱碳、D2烧结、E1施加外接线端、E2烘烤。
图2示出多层可变电阻的结构，其包含内电极(1)、可变电阻陶瓷材料(2)和外接线端(3)。
在一种实施方案中，该多层可变电阻的陶瓷体呈整块陶瓷体存在。
图3左方示出ECD脉冲的特性曲线，右方示出8/20脉冲的特性曲线。
多层可变电阻的制备按图1进行。
这些组分以氧化物形式、溶解形式或化合物的形式按表1所述的比例称重(A1)、预研磨(A2)、干燥(A3)、筛分(A4)和接着在400℃－1000℃间煅烧(A5)、后研磨(A6)、喷雾干燥(A7)和筛分(A8)。
由以此方法制备的粉末通过加入粘合剂、分散剂以及溶剂来制备浆料(B1)，由该浆料拉制层厚度为5－60 μm的膜(B2)，之后按类似图1的工艺图将该膜加工成多层可变电阻：在此所述坯膜经导电膏印制(C1)、经叠置和接着经剪切(C2, C3)。
在后续的脱碳步骤(D1)中，在180℃－500℃的温度从坯件中烧尽粘合剂，并在1100℃－1400℃的温度烧结该构件(D2)。接着涂覆外接线层(E1)，并在500℃－1000℃的温度烘烤该层(E2)。
在一种优选的方案中，方法步骤D2)的烧结温度为1100℃－1400℃。
在另一种优选的方案中，方法步骤E2)的烘烤温度为600℃－1000℃。
图2以侧视示意图示出一种多层构件。其中内电极(1)和可变电阻陶瓷材料(2)的层交替叠置。该内电极(1)交替分别与一个或另一个外接线端(3)连接。在中间范围内电极(1)搭接。
图2示出一种0402型多层可变电阻(尺寸为1.0 mm x 0.5 mm x 0.5 mm)的典型结构：其中内电极(2)的搭接面积以及内电极的数目可与所希望的电构件特性相适配。
该构件的电特性通过测定漏电流、可变电阻电压、非线性系数、8/20脉冲稳定性、ESD脉冲稳定性、在1 A下的8/20端电压(UK)来表征。
图3的左方和右方各示出脉冲曲线。图中均为电流I与时间t的关系曲线。
比可变电阻电压EV在1 mA下测定。
电容在1 V和1 kHz下测量。
ESD稳定性用图3左方的脉冲测定：为此对构件加载+/- 10 ESD脉冲(见图3右方)。脉冲前和后的UV的百分比变化以及脉冲前和后的漏电流的百分比变化以百分数计算，并且不允许有大于10 %的百分比变化。此外，进行了8/20的耐用性实验(脉冲形状见图3右方)。在此对构件加载在1 A，5 A，10 A，15 A，20 A和25 A的8/20脉冲(见图3右方)，并测定加载后的可变电阻电压及漏电流的百分比变化。
非线性系数按下列方程确定：
α1 (10 μA / 1 mA) = log (1*10-3 / 10*10-6) / log (V10mA / V10μA)
α2 (1 mA / 1A) = log (1 / 1*10-3) / log (V1A / V1mA)
α3 (1 mA / 20 A) = log (20 / 1*10-3) / log (V20A / V1mA)。
稳定性实验于125℃的80 % AVR下进行。在此条件下的漏电流IL不应具有升高特性。
表1 称量(单位为原子%)
  A B C D
Zn 97.9 97.4 96.9 96.4
Co 1.5 1.5 1.5 1.5
Pr 0.5 0.5 0.5 0.5
Cr 0.1 0.1 0.1 0.1
Ca 0.02 0.02 0.02 0.02
Si 0.02 0.02 0.02 0.02
Y 0 0.5 1 1.5
B 0.01 0.01 0.01 0.01
Al 60 ppm 60 ppm 60 ppm 60 ppm
表2 电结果
Figure 396954DEST_PATH_IMAGE001
 。
电数据综合于表2。通过加入钇使比可变电阻电压从268 V/mm升高到525 V/mm，同时相对介电常数下降。该变化归因于钇化合物阻止晶粒生长的特性。
为得到与晶粒相关的参数，计算εr / EV的比值。表2表明，该比值随钇加入量增加而下降。同时在同样好的非线性下得到高的ESD稳定性和8/20稳定性。
在一种实施方案中， Zn的含量优选大于90原子%，其中Zn优选以Zn2+存在。
在一种实施方案中，Pr的含量优选为0.5－0.6原子%，其中Pr优选以Pr3+/4+存在。
在一种实施方案中，M的含量优选为1－5原子%，其中M优选以M2+ / M3+ / M4+存存。
在一种实施方案中，Co的含量优选为1.5－2.0原子%，其中Co优选以Co2+存在。
在一种实施方案中，Ca的含量优选为0.01－0.03原子%，其中Ca优选以Ca2+存在。
在一种实施方案中，Si的含量优选为0.01－0.15原子%，其中Si优选以Si4+存在。
在一种实施方案中，Al的含量优选为0.005－0.01原子%，其中Al优选以Al3+存在。
在一种实施方案中，Cr的含量优选为0.05－0.2原子%，其中Cr优选以Cr3+存在。
在一种实施方案中，B的含量优选为0.001－0.01原子%，其中B优选以B3+存在。
在一种实施方案中，相对介电常数εr低于1000。
由于避免了碱金属碳酸盐的加入，在工业规模生产程序中可达高的可重复性。
在制备方法中可由合适的前体在高温下释出氧化硼作为烧结助剂，以为控制结构形态而进一步避免蒸发损失。
构型为0420和0210的多层可变电阻的特征在于其在漏电流、ESD稳定性、8/20耐用性、长期稳定性和非线性方面的优异结果。
主组分意指至少50原子%的含量。Zn的含量优选大于70原子%，其中Zn优选以Zn2+存在。
在可变电阻陶瓷的制备方法的一种方案中，该制备方法包括下列方法步骤：a)粗陶瓷材料的煅烧，b) 浆料制备，c) 制成坯膜，d) 坯膜脱粘合剂，和e)来自d）的坯膜的烧结。
在该制备方法的另一种方案中，该方法还包括方法步骤d)和e)之间的方法步骤d1)即构件的构成。
标号表：
1) 内电极
2) 可变电阻陶瓷材料
3) 外接线端。

Claims (15)

1.可变电阻陶瓷，其包含下列材料：
- Zn作为主组分，
- 含量达0.1－3原子%的Pr，
- 选自Y、Ho、Er、Yb、Lu的金属M，其含量达0.1－5原子%。
2.权利要求1的可变电阻陶瓷，其中M是Y或Lu。
3.前述权利要求之一的可变电阻陶瓷，其还包含含量达0.1－10原子%的Co。
4.前述权利要求之一的可变电阻陶瓷，其还包含含量达0.001－5原子%的Ca。
5.前述权利要求之一的可变电阻陶瓷，其还包含含量达0.001－0.5原子%的Si。
6.前述权利要求之一的可变电阻陶瓷，其还包含含量达0.001－0.1原子%的Al。
7.前述权利要求之一的可变电阻陶瓷，其还包含含量达0.001－5原子%的Cr。
8.前述权利要求之一的可变电阻陶瓷，其还包含含量达0.001－5原子%的B。
9.前述权利要求之一的可变电阻陶瓷，其包含
- Zn作为主组分，
含量达0.1－3原子%的Pr，
含量达0.1－5原子%的M，
含量达0.1－10原子%的Co，
含量达0.001－5原子%的Ca，
含量达0.001－0.5原子%的Si，
含量达0.001－0.1原子%的Al，
含量达0.001－5原子%的Cr，
含量达0.001－5原子%的B。
10.前述权利要求之一的可变电阻陶瓷，其相对介电常数εr小于2000。
11.前述权利要求之一的可变电阻陶瓷，其中通过加入M降低该可变电阻材料的相对介电常数。
12.前述权利要求之一的可变电阻陶瓷，其烧结温度为1000－1300℃。
13.前述权利要求之一的可变电阻陶瓷，其不含碱金属。
14.包含权利要求1－13之一的可变电阻陶瓷的多层构件，其具有用于ESD保护的构型。
15.用于制备权利要求1－13之一的可变电阻陶瓷的方法，其包括下列方法步骤：
a) 粗陶瓷材料的煅烧， 
b) 浆料制备，
c) 制成坯膜，
d) 坯膜脱粘合剂，
e) 来自d）的坯膜的烧结。
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