CN107240466B - 电压非线性电阻元件及其制法 - Google Patents

电压非线性电阻元件及其制法 Download PDF

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CN107240466B
CN107240466B CN201710186997.8A CN201710186997A CN107240466B CN 107240466 B CN107240466 B CN 107240466B CN 201710186997 A CN201710186997 A CN 201710186997A CN 107240466 B CN107240466 B CN 107240466B
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zinc oxide
voltage nonlinear
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oxide ceramic
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CN107240466A (zh
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石川昌树
早濑彻
小林义政
森本健司
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NGK Insulators Ltd
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Abstract

本发明提供一种电压线性电阻元件及其制法,其在氧化锌区域与其它的金属氧化物区域相接的结构的电压非线性电阻元件中,与以往相比增大电压非线性指数。电压非线性电阻元件(10)具备电压非线性电阻体(简称为电阻体)(20)、以及将该电阻体(20)夹在中间的一对电极(14)、(16)。电阻体(20)是将以氧化锌为主要成分的第1层(21)、同样地以氧化锌为主要成分的第2层(22)、以及以不同于氧化锌的金属氧化物为主要成分的第3层(23)进行层叠而得到的结构。第2层(22)与第1层(21)相接,厚度比第1层(21)薄,体积电阻率高于第1层(21)。第3层(23)与第2层(22)相接。

Description

电压非线性电阻元件及其制法
技术领域
本发明涉及电压非线性电阻元件及其制法。
背景技术
电压非线性电阻元件(压敏电阻元件)是由一对电极夹持了电压非线性电阻体的结构的元件,作为保护电子电路等不受异常电压损害的元件而被广泛应用于湿度传感器、温度传感器等各种传感器。作为这种电压非线性电阻元件,在专利文献1中公开了一种元件,其具有以氧化锌为主要成分的区域与包含铋-碱土金属-铜的复合氧化物的区域的接合部。该电压非线性电阻元件通过以下的制法而制造。首先,利用通常的成形方法将氧化锌粉体成形,在大气中、1250℃烧成2小时。其后,对烧结体的两面进行研磨,特别是使用氧化铝微粉对其一面进行镜面研磨。其后用有机溶剂充分洗涤,然后使用高频溅射装置,在氧化锌烧结体的经过镜面研磨的面上形成Bi-碱土金属-Cu氧化物的溅射膜。接着在870℃的氧气气氛中进行24小时的热处理。
现有技术文献
专利文献
专利文献1:日本特公平7-111922号公报
发明内容
发明想要解决的课题
关于电压非线性指数,是在将电压非线性电阻元件与所要保护的电路并联连接的情况下,表示在正常运作时在电路侧流通的电流量的指标。电压非线性指数越大,则在正常运作时电流越在电路侧流通,因而能够实现节能化。但是,专利文献1的电压非线性电阻元件存在有如下的问题:电压非线性指数仅为约8,无法充分实现节能化。
本发明为了解决这样的课题而完成,主要目的在于,在氧化锌区域与其它的金属氧化物区域相接的结构的电压非线性电阻元件中,与以往相比增大电压非直线指数。
用于解决问题的方案
本发明的电压非线性电阻元件具备:
以氧化锌为主要成分的第1层,
以氧化锌为主要成分的第2层,其与前述第1层相接,并且与前述第1层相比厚度薄且体积电阻率高,
以不同于氧化锌的金属氧化物为主要成分的第3层,其相接于前述第2层的与前述第1层相接一侧的相反侧。
在该电压非线性电阻元件中,在以氧化锌为主要成分的第1层与以不同于氧化锌的金属氧化物为主要成分的第3层之间,存在有以氧化锌为主要成分并且与第1层相比厚度薄且体积电阻率高的第2层。由于存在该第2层,使得电压非线性指数与以往相比变大。其结果是,在通常时即低电压时,电流不易流通于与要保护的电路并联连接的电压非线性电阻元件,能够实现节能化。
予以说明的是,主要成分是指最多地包含的成分,例如是指质量比例最高的成分。
在本发明的电压非线性电阻元件中,前述第1层的体积电阻率优选为1×10-2Ωcm以下,前述第2层的体积电阻率优选为1×103Ωcm以下。如果这样设定,则电压非线性指数变得充分大。第1层的体积电阻率更优选为6×10-4Ωcm以下,第2层的体积电阻率更优选为2×10-3Ωcm以下。如果这样设定,则对与要保护的电路并联连接的电压非线性电阻元件施加浪涌电压时,能够使大的电流流通于电压非线性电阻元件。因此,电路的保护效果变高。
在本发明的电压非线性电阻元件中,前述第2层的厚度优选为0.2~300nm。如果这样设定,则电压非线性指数变得充分大。
在本发明的电压非线性电阻元件中,前述第1层也可以含有选自由Al、Ga以及In组成的组中的至少1种金属元素的氧化物。通过添加这样的三价的金属离子,从而能够比较容易地使以氧化锌为主要成分的第1层的体积电阻率成为低电阻。
在本发明的电压非线性电阻元件中,前述第3层优选以选自由Sr、Bi以及Pr组成的组中的1种金属元素的氧化物为主要成分,并含有选自由Si、Cr、Mn、Co、Ni、Za、Sb以及La组成的组中的至少1种金属元素的氧化物。如果这样设定,则通过改变向作为主要成分的金属氧化物中添加的其它金属氧化物的金属种类、添加量,从而能够制成具有各种特性的电压非线性电阻元件。
本发明的电压非线性电阻元件的制法是制造上述的任一种电压非线性电阻元件的方法,包含如下的工序:
(a)通过将氧化锌粉末的成形体在非氧化气氛下烧成而制作氧化锌陶瓷基板的工序,所述氧化锌粉末还可以包含选自由Al、Ga以及In组成的组中的至少1种金属元素,
(b)通过将前述氧化锌陶瓷基板在氧化气氛下烧成而使前述氧化锌陶瓷基板的表层变为与前述氧化锌陶瓷基板的内部相比体积电阻率高的层,从而分别将前述氧化锌陶瓷基板的内部以及表层制成前述第1层以及前述第2层的工序,或者,
通过在前述氧化锌陶瓷基板的表面成膜以氧化锌为主要成分并且与前述氧化锌陶瓷基板相比厚度薄且体积电阻率高的氧化锌层,从而分别将前述氧化锌陶瓷基板以及氧化锌层制成前述第1层以及前述第2层的工序,以及
(c)在前述第2层的表面形成前述第3层的工序。
根据该制法,能够容易地制造上述的电压非线性电阻元件。
附图说明
图1是电压非线性电阻元件10的截面图。
图2是电压非线性电阻元件10的制造工序图。
附图标记说明
10:电压非线性电阻元件,14、16:电极,20:电阻体,21:第1层,22:第2层,23:第3层,31:氧化锌陶瓷薄板。
具体实施方式
一边参照附图一边在以下说明本发明的优选实施方式。图1为本实施方式的电压非线性电阻元件10的截面图。
电压非线性电阻元件10具备电压非线性电阻体(简称为电阻体)20、以及将该电阻体20夹在中间的一对电极14、16。
电阻体20是将以氧化锌为主要成分的第1层21、同样地以氧化锌为主要成分的第2层22、以及以不同于氧化锌的金属氧化物为主要成分的第3层23层叠而得到的结构。第2层22与第1层21相接,厚度比第1层21薄,载流子浓度低于第1层21。第3层23与第2层22相接。予以说明的是,第1层21的侧面21a以及下表面21b可以是与第1层21相同的组成,也可以是与第2层22相同的组成。
第1层21的体积电阻率优选为1.0×10-2Ωcm以下,更优选为1.0×10-3Ωcm以下,进一步优选为6.0×10-4Ωcm以下。第2层22的体积电阻率高于第1层21的体积电阻率,优选为1×103Ωcm以下,更优选为3×102Ωcm以下,进一步优选为2×10-3Ωcm以下。第2层22的厚度没有特别限定,但是优选为0.2~300nm,更优选为0.2~10nm,进一步优选为1~10nm。第1层21也可以含有选自由Al、Ga以及In组成的组中的至少1种金属元素的氧化物。第3层23优选以选自由Sr、Bi以及Pr组成的组中的1种金属元素的氧化物为主要成分,并含有选自由Si、Cr、Mn、Co、Ni、Za、Sb以及La组成的组中的至少1种金属元素的氧化物。
电极14按照与第1层21的外表面接触的方式形成,电极16按照与第3层23的外表面接触的方式形成。对于电极14、16,只要是显示出与氧化锌陶瓷良好的欧姆特性的电传导性好的材料就没有特别限定,例如可列举金、银、铂、铝等。
接着,在以下说明电压非线性电阻元件10的制造例。图2为电压非线性电阻元件10的制造工序图。
·氧化锌陶瓷薄板的制作(参照图2的工序(a))
氧化锌陶瓷薄板31的体积电阻率优选为1.0×10-2Ωcm以下,更优选为1.0×10-3Ωcm以下,进一步优选为6.0×10-4Ωcm以下。这样的氧化锌陶瓷薄板31,可通过将作为掺杂剂的Al、Ga、In等的三价的离子固溶于氧化锌陶瓷,或通过将氧化锌粉末在非氧化气氛下烧成而导入氧缺陷来获得。为了获得使掺杂剂固溶了的氧化锌陶瓷薄板31,首先,将Al2O3、Ga2O3、In2O3等三价的金属氧化物粉末按照成为0.05~2.0质量%的方式混合于氧化锌粉末中,成形为形成预定形状的成形体。接着,将该成形体在非氧化气氛(例如氮气气氛、氩气气氛)下,在900~1200℃保持了数小时,然后进一步升温到1300~1500℃而烧成数小时。通过这样设定,从而能够比较容易地获得氧化锌陶瓷薄板31。为了制成设为目标的载流子浓度、体积电阻率,调整混合于氧化锌粉末中的三价的金属氧化物粉末的质量%,或调整烧成温度即可。另外,用于原料的氧化锌粉末的平均粒径(利用激光衍射法测得,下同)优选为0.02~5μm。三价的金属氧化物粉末的平均粒径优选为0.01~0.5μm。另一方面,为了将氧化锌粉末在非氧化气氛下烧成而获得体积电阻率低的氧化锌陶瓷薄板31,例如,将氧化锌粉末在非氧化气氛(例如氮气气氛、氩气气氛)下,在1300~1500℃保持数小时而烧成。这样的氧化锌陶瓷薄板31也可从利用同样的方法制作的氧化锌陶瓷块体切出。
·高体积电阻层的制作(参照图2的工序(b))
(其一)
通过将氧化锌陶瓷薄板31在氧化气氛(例如氧气气氛、大气气氛)下烧成,从而使氧化锌陶瓷薄板的各面的表层变为与氧化锌陶瓷薄板的内部相比体积电阻率高的层。其结果是,氧化锌陶瓷薄板31的内部成为第1层21,各个面的表层成为第2层22。第1层21以及第2层22的体积电阻率如上所述。烧成温度优选为600~1000℃,更优选为700~900℃。关于烧成时间,按照第1层21以及第2层22的体积电阻率落入上述的数值范围的方式而适当设定即可,例如也可在0.1~1小时的范围设定。
(其二)
在氧化锌陶瓷薄板31的上表面成膜以氧化锌为主要成分并且与氧化锌陶瓷薄板31相比厚度薄且体积电阻率高的氧化锌层。其结果是,氧化锌陶瓷薄板31以及氧化锌层分别成为第1层21以及第2层22。第1层21以及第2层22的体积电阻率如上所述。氧化锌层为单一氧化锌的情况下,例如,可以将氧化锌设为靶,利用溅射在氧化锌陶瓷薄板上形成氧化锌层。除了溅射之外也可以使用真空蒸镀、离子镀等。在氧化锌层包含副成分的情况下,也可以除了氧化锌之外还使用副成分作为靶,利用多元同时溅射在氧化锌陶瓷薄板上形成氧化锌层。或者,也可以将含有氧化锌粉末的糊剂涂布于氧化锌陶瓷薄板,进行干燥,在比较低的温度(例如200~700℃,优选为200~500℃)进行热处理而制成氧化锌层。
·金属氧化物层的制作(参照图2的工序(c))
金属氧化物层(第3层23)可以是单一氧化铋,但是也可以以氧化铋作为主要成分并且包含其它的氧化物(例如Sb2O3、Cr2O3、MnO、CoO、ZnO、SiO2等)作为副成分。氧化铋层为单一氧化铋的情况下,例如,也可以将氧化铋作为靶,在第2层22上利用溅射而形成氧化铋层作为第3层23。除了溅射之外也可以使用真空蒸镀、离子镀等。或者,也可以将含有氧化铋粉末的糊剂涂布于第2层22,进行干燥,在比较低的温度(例如为200~700℃,优选为200~500℃)进行热处理从而形成氧化铋层作为第3层23。另一方面,在氧化铋层包含副成分的情况下,也可以除了氧化铋之外还使用副成分作为靶,利用多元同时溅射在第2层22上形成氧化铋层作为第3层23。或者,也可以将除了氧化铋粉末之外还含有副成分的粉末的糊剂涂布于第2层22,进行干燥,在比较低的温度进行热处理从而形成氧化铋层作为第3层23。也可以使用氧化锶、氧化镨来替代氧化铋。
·电极14、16的制作(参照图2的工序(d))
关于电极14、16,可以通过在包含第1层21~第3层23的电阻体20的两面蒸镀或者溅射电极材料来制作。作为电极材料,可列举金、银、铂、铝等。或者,也可以准备板状的电极14、16,也可以将它们介由导电性接合材料而接合于电阻体20的各面上。
根据以上详述的电压非线性电阻元件10,在以氧化锌为主要成分的第1层21与以不同于氧化锌的金属氧化物为主要成分的第3层23之间,设置有以氧化锌为主要成分并且与第1层21相比厚度薄且体积电阻率高的第2层22。通过设置该第2层22,从而电压非线性指数与以往相比变大。其结果是,在通常时即低电压时,电流不易流通于与要保护的电路并联连接的电压非线性电阻元件10,能够实现节能化。
予以说明的是,自不用言,本发明不受上述实施方式的任何限定,只要属于本发明的技术范围就可以以各种实施方式实施。
例如,在上述的电压非线性电阻元件10中,在1个电阻体20的两面设置了电极14、16,但也可以在层叠多个电阻体20而得到的层叠体的两面设置电极。通过使用这样的层叠型电阻体,可以控制压敏电阻电压,能够获得适合用途的压敏电压的电压非线性电阻元件。
实施例
[实施例1]
向氧化锌(平均粒径1.5um)中添加1质量%的氧化镓(平均粒径0.02μm),进行湿式混合后,进行蒸发干燥,使其通过网眼75μm的筛子后进行成形。将成形体进行脱脂后,在N2气氛、1100℃下保持5小时,然后进一步升温到1300℃,进行5小时烧成,制作了氧化锌陶瓷块体。该氧化锌陶瓷块体的体积电阻率为6.0×10-4Ωcm。予以说明的是,体积电阻率利用四端子法进行测定。
将所获得的氧化锌陶瓷块体切成5mm×5mm×1mm的板状,得到氧化锌陶瓷薄板。对该薄板的上表面进行研磨、洗涤后,在氧气气氛、800℃下保持0.5小时,从而获得各面的表层被氧化了的氧化锌陶瓷薄板。表层的体积电阻率为2.0×10-3Ωcm,厚度为0.2(nm)。氧化锌陶瓷薄板中除了表层以外的内部相当于第1层,表层相当于第2层。予以说明的是,第2层的体积电阻率利用四端子法(端子间距10μm)进行测定。第2层的厚度如下求出。即,另行将氧化锌陶瓷薄板在氧气(18O)气氛下,在与上述相同的条件(在800℃、0.5小时)下保持后,使用二次离子质谱仪测定氧化锌陶瓷薄板的18O的深度方向分布,求出第2层的厚度。氧化锌陶瓷薄板中的氧原子由16O构成,相对于此,在作为16O的同位素的18O气氛下进行热处理时会被18O氧化,因而第2层的厚度可根据18O的深度方向分布而求出。
接着,使用包含铋、锰、钴的氧化物作为靶(作为金属元素比,铋:锰:钴=60:20:20),进行高频等离子体溅射,在氧化锌陶瓷薄板的上表面成膜包含铋、锰、钴的氧化物的溅射膜(厚度0.3μm)。该溅射膜相当于第3层。通过这样操作,获得了由3层结构形成的电阻体。对于溅射,使用了ULVAC机工制的RFS-200。成膜条件如下所示。靶尺寸:直径80mm,RF输出功率:40W,气压(O2):5.0Pa,成膜时间:120分钟。
在所获得的电阻体的两面上设置Al蒸镀电极,得到电压非线性电阻元件。对该电压非线性电阻元件的两个电极施加电压而测定电流-电压特性。予以说明的是,将设置于氧化锌陶瓷薄板侧的电极设为阳极,将设置于氧化铋的溅射膜的电极设为阴极。遵照IEC61051-1,使用Agilent Technologies公司制的Agilent B2901A来测定电流-电压特性。基于电流-电压特性,使用下述式(1)而求出1μA~1mA的电压非线性指数。式(1)中,V1μA为电流1μA时的电压,V1mA为电流1mA时的电压。通过这样操作而求得的电压非线性指数为24。将实施例1的特征、电压非线性指数示于表1。予以说明的是,在表1中还示出后述的实施例2~4、比较例1~3的特征、电压非线性指数。
电压非线性指数=log(1μA/1mA)/log(V1μA/V1mA)···(1)
表1
Figure BDA0001255076940000081
[实施例2]
将在实施例1中对上表面进行了研磨、洗涤的氧化锌陶瓷薄板在氧气气氛、900℃下保持0.5小时,除此以外,与实施例1同样地操作而制作了电压非线性电阻元件。第2层的厚度为2nm。根据所获得的元件的电流-电压特性,求出1μA~1mA之间的电压非线性指数,结果为24。将实施例2的特征、电压非线性指数示于表1。
[实施例3]
在实施例1中,将向氧化锌中添加的氧化镓的量变更为0.05质量%,除此以外,与实施例1同样地操作而制作了电压非线性电阻元件。第1层以及第2层的体积电阻率分别为6×10-3Ωcm、3×10-2Ωcm。根据所获得的元件的电流-电压特性,求出1μA~1mA之间的电压非线性指数,结果为18。将实施例3的特征、电压非线性指数示于表1。
[实施例4]
通过与实施例1同样的方法制作氧化锌陶瓷块体,从那里切出氧化锌陶瓷薄板。接着,使用氧化锌作为靶,进行高频等离子体溅射,在氧化锌陶瓷薄板的上表面成膜厚度为300nm的氧化锌的溅射膜。氧化锌陶瓷薄板相当于第1层,氧化锌的溅射膜相当于第2层。对于溅射,使用了ULVAC机工制的RFS-200。成膜条件如下所示。靶尺寸:直径80mm,RF输出功率:40W,气压(N2):5.0Pa,成膜时间:150分钟。
由此获得的氧化锌溅射膜的体积电阻率为3×102(Ωcm),厚度为300(nm)。接着,通过与实施例1同样的方法在氧化锌溅射膜上成膜包含铋、锰、钴的氧化物。该溅射膜相当于第3层。通过这样操作而获得了由3层结构形成的电阻体。在所获得的电阻体的两面上设置Al蒸镀电极,得到电压非线性电阻元件。根据该元件的电流-电压特性,求出1μA~1mA之间的电压非线性指数,结果为11。将实施例4的特征、电压非线性指数示于表1。
予以说明的是,体积电阻率如下测定,在玻璃基板上以与实施例2相同的组成、成膜条件形成氧化锌溅射膜,使用该带有氧化锌溅射膜的玻璃基板并且利用东阳Technica公司制的ResiTest8300(商品名)进行测定。对于第2层的厚度,利用TEM(透射型电子显微镜)观察3层结构体而进行测定。在TEM中,因第1层与第2层中氧化锌的结晶取向不同而能够区别两层的边界,因第2层与第3层的元素种类不同而能够区别边界。
[实施例5]
在实施例1中,在成膜第3层时,使用包含铋、钴的氧化物(作为金属元素比,铋:钴=50:50)作为靶,除此以外,与实施例1同样地操作而制作了电压非线性电阻元件。根据该元件的电流-电压特性,求出1μA~1mA之间的电压非线性指数,结果为11。将实施例5的特征、电压非线性指数示于表1。
[实施例6]
在实施例1中,在成膜第3层时,使用包含镨、钴的氧化物(作为金属元素比,镨:钴=50:50)作为靶,除此以外,与实施例1同样地操作而制作了电压非线性电阻元件。根据该元件的电流-电压特性,求出1μA~1mA之间的电压非线性指数,结果为10。将实施例6的特征、电压非线性指数示于表1。
[比较例1]
在实施例1中,省略了将氧化锌陶瓷薄板的各面表层氧化的工序,除此以外,通过与实施例1同样的方法制作了电阻体。该电阻体是没有第2层的2层结构体。在该电阻体的两面上设置Al蒸镀电极,得到电压非线性电阻元件。根据该元件的电流-电压特性,求出1μA~1mA之间的电压非线性指数,结果为3。将比较例1的特征、电压非线性指数示于表1。
[比较例2]
在实施例1中,作为氧化锌陶瓷块体的原料,仅使用氧化锌而不添加氧化镓,制作氧化锌陶瓷块体,从该块体切出了氧化锌陶瓷薄板,除此以外,通过与实施例1同样的方法制作了电压非线性电阻元件。与氧化锌陶瓷薄板的内部(第1层)相比,氧化锌陶瓷薄板的表层(第2层)的体积电阻率更低。根据所获得的电压非线性电阻元件的电流-电压特性,求出1μA~1mA之间的电压非线性指数,结果为8。将比较例2的特征、电压非线性指数示于表1。
[比较例3]
在实施例2中,在氧化锌陶瓷薄板的上表面成膜氧化锌的溅射膜时,将溅射膜的厚度设为1mm,除此以外,通过与实施例2同样的方法制作了电压非线性电阻元件。根据该元件的电流-电压特性,求出1μA~1mA之间的电压非线性指数,结果为7。将比较例3的特征、电压非线性指数示于表1。
予以说明的是,上述的实施例只不过是本发明的一个例子,本发明不限于这些实施例。

Claims (7)

1.一种电压非线性电阻元件,其具备:
以氧化锌为主要成分的第1层,
以氧化锌为主要成分的第2层,其与所述第1层相接,并且与所述第1层相比厚度薄且体积电阻率高,以及
以不同于氧化锌的金属氧化物为主要成分的第3层,其相接于所述第2层的与所述第1层相接一侧的相反侧,
所述第1层的体积电阻率为6.0×10-4Ωcm以下,所述第2层的体积电阻率为2×10-3Ωcm以下,
所述第3层由氧化铋、氧化锰和氧化钴构成。
2.根据权利要求1所述的电压非线性电阻元件,其中,所述第2层的厚度为0.2~300nm。
3.根据权利要求1或2所述的电压非线性电阻元件,其中,所述第1层含有选自由Al、Ga以及In组成的组中的至少1种金属元素的氧化物。
4.一种电压非线性电阻元件的制法,其为制造权利要求1~3中任一项所述的电压非线性电阻元件的方法,包含如下的工序:
(a)通过将氧化锌粉末的成形体在非氧化气氛下烧成而制作氧化锌陶瓷基板的工序,
(b)通过将所述氧化锌陶瓷基板在氧化气氛下烧成而使所述氧化锌陶瓷基板的表层变为与所述氧化锌陶瓷基板的内部相比体积电阻率高的层,从而分别将所述氧化锌陶瓷基板的内部以及表层制成所述第1层以及所述第2层的工序,以及
(c)在所述第2层的表面形成所述第3层的工序。
5.根据权利要求4所述的电压非线性电阻元件的制法,所述氧化锌粉末还包含选自由Al、Ga以及In组成的组中的至少1种金属元素的氧化物。
6.一种电压非线性电阻元件的制法,其为制造权利要求1~3中任一项所述的电压非线性电阻元件的方法,包含如下的工序:
(a)通过将氧化锌粉末的成形体在非氧化气氛下烧成而制作氧化锌陶瓷基板的工序,
(b)通过在所述氧化锌陶瓷基板的表面成膜以氧化锌为主要成分并且与所述氧化锌陶瓷基板相比厚度薄且体积电阻率高的氧化锌层,从而分别将所述氧化锌陶瓷基板以及氧化锌层制成所述第1层以及所述第2层的工序,以及
(c)在所述第2层的表面形成所述第3层的工序。
7.根据权利要求6所述的电压非线性电阻元件的制法,所述氧化锌粉末还包含选自由Al、Ga以及In组成的组中的至少1种金属元素的氧化物。
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