CN106431390A - 半导体陶瓷组合物和ptc热敏电阻 - Google Patents

半导体陶瓷组合物和ptc热敏电阻 Download PDF

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CN106431390A
CN106431390A CN201610627105.9A CN201610627105A CN106431390A CN 106431390 A CN106431390 A CN 106431390A CN 201610627105 A CN201610627105 A CN 201610627105A CN 106431390 A CN106431390 A CN 106431390A
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ceramic composition
resistivity
semiconductive ceramic
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ratio
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CN106431390B (zh
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藤田孝
藤田一孝
伊藤和彦
志村寿
志村寿一
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TDK Corp
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Abstract

本发明提供一种即使在大气中烧结也可以容易地半导体化，常温电阻率小，即使长时间通电也可以抑制电阻值的经时劣化，并且耐受电压大的居里温度为120℃以上的BaTiO3系半导体陶瓷组合物以及PTC热敏电阻。所述半导体陶瓷组合物以式(1)所表示的化合物作为主成分。(BavBixAyREw)m(TiuTMz)O3(1)(A为Na和K，RE为选自Y、La、Ce、Pr、Nd、Sm、Gd、Dy和Er中的至少1种，TM为选自V、Nb和Ta中的至少1种)、0.01≤x≤0.15(2)、x≤y≤0.3(3)、0≤(w+z)≤0.01(4)、v+x+y+w＝1(5)、u+z＝1(6)、0.950≤m≤1.050(7)，进一步含有0.001～0.055mol的Ca，Na/(Na+K)的比为0.1以上且小于1。

Description

半导体陶瓷组合物和PTC热敏电阻
技术领域
本发明涉及一种用于加热器元件或过热检测元件等中的半导体陶瓷组合物和PTC热敏电阻。
背景技术
作为热敏电阻之一，已知有具有正的电阻温度系数的PTC(Positive TemperatureCoefficient)热敏电阻。该PTC热敏电阻由于相对于温度的上升电阻增加，因此，可以利用为自控制型加热器元件、过电流保护元件、过热检测元件等。一直以来，PTC热敏电阻是在主成分的钛酸钡(BaTiO3)中添加微量的稀土元素等并使之半导体化而成的，在低于居里点时为低电阻，但是在高于居里点时经过几个数量级急剧地高电阻化。
BaTiO3的居里点通常为约120℃，通过用Sr或Sn和Zr置换一部分Ba和Ti，可以使居里点向低温侧移动。特别是用作加热器元件的PTC热敏电阻由于在高温下使用，因此，要求居里点高。然而，对于居里点向高温侧移动，现状是用Pb置换一部分Ba，从社会的环境负荷降低的趋势出发也要求不使用Pb的替代材料的实用化。
在下述专利文献1中显示了一种半导体陶瓷组合物的制造方法，其中，在不用Pb而用(BiNa)置换一部分Ba得到的Ba1-2X(BiNa)XTiO3(0<X≤0.15)而成的组合物中添加Nb、Ta或稀土元素中的任意一种以上，在氮气中烧结之后，在氧化性气氛中进行热处理。
另外，在下述专利文献2中显示了一种半导体陶瓷组合物的制造方法，其中，对于用Bi和碱金属A1(Na、K和Li中的至少1种)置换BaTiO3的一部分Ba而成的半导体陶瓷组合物，作为抑制长时间通电之后的电阻值的电阻变化率的方法，使上述组合物的烧结体的相对于理论密度的实测密度(以下称为“相对密度”)为70～90％。
上述任一的专利文献都记载了不使用Pb而将居里点向高于120℃的高温侧移动，从而可以得到常温电阻率小的半导体陶瓷组合物。
现有技术文献
专利文献
专利文献1：日本特开昭56-169301号公报
专利文献2：日本特开2012-209292号公报
发明内容
发明所要解决的技术问题
在上述专利文献1中有关于在Ba1-2X(BiNa)XTiO3(0<X≤0.15)而成的组合物中添加Nd在氮气中进行烧结之后，在氧化性气氛中进行了热处理的结果的记载。然而，对于添加了其它半导体化剂的情况没有详细的记载，对于相对于特性的添加剂效果和其程度不明确。另外，由于在大气中烧结时不能半导体化，因此，与大气中烧结的情况相比较，有制造成本变高的问题。
上述专利文献2所记载的半导体陶瓷组合物通过将烧结体的相对密度调节为70～90％，从而相对于使电阻变化率△ρ/ρ0为无调节状态的67％，可以抑制直至28％，但是实用上期望使之进一步降低。
另外，作为电阻变化率△ρ/ρ0的定义，在上述专利文献2中作为通电试验施加20V的直流电压1000小时之后，在环境温度为25℃下测定试验前的电阻率ρ0和试验后的电阻率ρ1，求得其差△ρ(＝ρ1-ρ0)，算出电阻变化率△ρ/ρ0。
PTC热敏电阻的常温电阻率，从节能的观点出发，寻求低电阻，但通常伴随着通电时间的长期化而经年劣化，有常温电阻率增大的倾向，因此，电阻变化率△ρ/ρ0在确保PTC热敏电阻的可靠性方面是重要的指标之一。
同时，今后需求扩大的电动汽车上搭载的PTC加热器中由于不通过变压器而施加高电压，因此，寻求优异的耐受电压。
因此，本发明的目的在于提供一种半导体陶瓷组合物以及具备其的PTC热敏电阻，其中，所述半导体陶瓷组合物是BaTiO3系的半导体陶瓷组合物，且是不使用Pb而使居里点向高于120℃的高温侧移动的半导体陶瓷组合物，而且在大气中或者氮气气氛中的任一种中进行烧结也可以容易地半导体化，保持能够将常温电阻率实用化的水平，并且电阻变化率△ρ/ρ0小，耐受电压优异。
解决技术问题的手段
本发明者们为了解决上述技术问题而进行了各种研究，其结果，通过在BaTiO3系的半导体陶瓷组合物中不用Pb而以规定的范围用Bi和碱金属(同时包含Na和K)来置换一部分Ba，并且将Ba位点/Ti位点的摩尔比、Ca添加量以及Na和K的比设定在规定的范围内，从而发现了一种半导体陶瓷组合物，其即使在大气中或者氮气气氛中的任一种中进行烧结也可以容易地进行半导体化，将常温电阻率控制在500Ωcm以下，将电阻变化率△ρ/ρ0控制在20％以下，并且耐受电压V0为400V/mm以上，居里点向高于120℃的高温侧发生了移动。
即，本发明为一种半导体陶瓷组合物，其特征在于，具备以下述通式(1)所表示的BaTiO3系化合物为主成分的烧结体，
(BavBixAyREw)m(TiuTMz)O3 (1)
上述通式(1)中，上述A同时包含Na和K这2种元素，上述RE为选自Y、La、Ce、Pr、Nd、Sm、Gd、Dy和Er中的至少1种元素，上述TM为选自V、Nb和Ta中的至少1种元素，w、x、y、z和m满足下述式(2)～(7)，
0.01≤x≤0.15 (2)
x≤y≤0.3 (3)
0≤(w+z)≤0.01 (4)
v+x+y+w＝1 (5)
u+z＝1 (6)
0.950≤m≤1.050 (7)
进一步，相对于1mol的Ti位点(Ti和TM的总摩尔数)，以元素换算以0.001mol以上且0.055mol以下的比例含有Ca，并且Na/(Na+K)的比为0.1以上且小于1。
本发明者们认为，作为发挥上述特性的理由，通过将Bi和碱金属A(同时包含Na和K)的添加量和比率设定在规定的范围并且A过量，从而过量的A促进半导体化，并且作为烧结助剂促进适度的晶粒生长，作为结果即使在大气中或者氮气气氛中的任一种中进行烧结也可以使居里点向高于120℃的高温侧移动，并且可以得到低电阻的半导体陶瓷组合物。另外，认为通过Ca固溶于Ba位点，从而碱金属A可以稳定地固溶于Ba位点中，因此，可以抑制通电时碱金属A离子的移动，可以减小电阻变化率△ρ/ρ0。另外，K固溶于Ba位点中，由于相比Na更稳定地固溶，因此，可以抑制碱金属A离子向晶界的析出，作为结果可以提高耐受电压。具体而言，可以得到将常温电阻率控制在500Ωcm以下，并且电阻变化率△ρ/ρ0为20％以下，耐受电压V0为400V/mm以上，并且居里点向高于120℃的高温侧发生了移动的半导体陶瓷组合物。但是，对于半导体化的机理，不限定于此。
另外，上述半导体陶瓷组合物优选相对于1mol的Ti位点(Ti和TM的总量：u+z)以元素换算以0.035mol以下的比例含有Si。通过在上述范围内含有Si，从而常温电阻率减少效果提高。
另外，上述半导体陶瓷组合物优选相对于1mol的Ti位点(Ti和TM的总量：u+z)以元素换算以0.0015mol以下的比例进一步含有Mn。通过在上述范围内含有Mn，从而有增大常温电阻率和超过居里点上升的电阻的变化幅度(以下方便起见称为“PTC突跳(PTC jump)”)的效果。另外，PCT突跳是用于判断PTC热敏电阻的能力的一个指标，作为Log10(280℃下的电阻率/常温电阻率)算出。另外，本发明中的常温电阻率是指25℃下的电阻率。
发明的效果
根据本发明，可以得到在BaTiO3系的半导体陶瓷组合物中不含Pb，即使在大气中或者氮气气氛中的任一种中进行烧结也可以容易地进行半导体化，将常温电阻率控制在500Ωcm以下，并且电阻变化率△ρ/ρ0小，耐受电压V0为400V/mm以上，居里点向高于120℃的高温侧发生了移动的半导体陶瓷组合物。具备上述半导体陶瓷组合物的PTC热敏电阻可以期待特别是在加热器元件中的应用。
附图说明
图1是表示具备本发明的实施方式所涉及的半导体陶瓷组合物的PTC热敏电阻的一个结构例的立体图。
符号的说明：
1 PTC热敏电阻
2 陶瓷素体
3a、3b 电极
具体实施方式
如图1所示，PTC热敏电阻1具备由本申请发明的BaTiO3系半导体陶瓷组合物构成的陶瓷素体2和在陶瓷素体的相对的两个主面上形成的电极3a和3b。作为电极3a和3b，可以以由Cu、Ni、Al、Cr、Zn、Ag、Ni-Cr合金、Ni-Cu等的导电性材料构成的一层结构或多层结构形成。
本发明所涉及的组合物，基于摩尔比的组合物具备以下述通式(1)所表示的BaTiO3系化合物为主成分的烧结体。
(BavBixAyREw)m(TiuTMz)O3 (1)
其中，以A同时包含Na和K，RE为选自Y、La、Ce、Pr、Nd、Sm、Gd、Dy和Er中的至少1种元素，TM为选自V、Nb和Ta中的至少1种元素所表示的物质为主成分，进一步含有Ca作为副成分。
上述式(1)中，分别表示用Bi、A、RE置换Ba位点的一部分的量、用TM置换Ti位点的一部分的量、进一步Ba位点与Ti位点的比的u、v、w、x、y、z和m满足下述式(2)～(7)。
0.01≤x≤0.15 (2)
x≤y≤0.3 (3)
0≤(w+z)≤0.01 (4)
v+x+y+w＝1 (5)
u+z＝1 (6)
0.950≤m≤1.050 (7)
进一步，对于(1)所表示的组合物，相对于1mol的Ti位点(Ti和TM的总摩尔数)，以元素换算以0.001mol以上且0.055mol以下的比例含有Ca。
另外，上述半导体陶瓷组合物进一步相对于1mol的通式(1)中的Ti位点(Ti和TM的总摩尔数)以元素换算优选以0.035mol以下的比例含有Si。进一步，更优选为0.005mol以上且0.02mol以下。在晶界析出的Si与同样在晶界微量析出的碱金属Na和K分别形成化合物，从而可以抑制通电时的碱金属Na和K离子的移动，因此，常温电阻率减少效果进一步提高。但是，如果Si超过0.035mol，则过量的Si元素在晶界大量偏析，从而有妨碍传导电子的移动并且常温电阻率上升的倾向。
另外，上述半导体陶瓷组合物进一步相对于1mol的Ti位点(Ti和TM的总摩尔数)以元素换算优选以0.0015mol以下的比例含有Mn。进一步，更优选为0.0002mol以上且0.0010mol以下。通过在上述范围内含有Mn，在晶界形成适度的受主能级，并且有PTC突跳的提高效果。但是，Mn如果超过0.0015mol，则传导电子的陷阱变得过量，有常温电阻率上升的倾向。
在通式(1)中，Bi的成分范围x为0.01≤x≤0.15。在x小于0.01时，由于Bi成分含量过少，因此，居里点没有向高温侧移动。另外，如果x超过0.15，则半导体化变得不充分，常温电阻率超过500Ωcm。另外，本发明中的居里点是指元件的电阻率与25℃的电阻率相比成为2倍的温度。
另外，在上述组成式中，A同时包含Na和K，y为x≤y≤0.3。在y<x时，耐受电压V0没有上升。另外，如果y超过0.3，则半导体化变得不充分，常温电阻率超过500Ωcm。
另外，在上述组成式中，Na与K的成分范围有关系，Na/(Na+K)的比优选为0.1以上且小于1的范围。在Na/(Na+K)的比小于0.1时，由于K过多，因此，半导体化变得不充分，常温电阻率超过500Ωcm。另外，在Na/(Na+K)的比为1的情况下，由于没有同时含有Na和K，因此，耐受电压V0变低。
另外，在上述组成式中，对于作为供体成分的RE和TM的总量：(w+z)，如果相对于1mol的Ti位点(Ti和TM的总摩尔数)为0.01mol以下，则有常温电阻率减少效果和耐受电压提高效果，也可以完全不含有。进一步，更优选为0.001mol以上且0.005mol以下。另外，如果(w+z)超过0.01，则过量的RE或TM在晶界偏析妨碍传导电子的移动，常温电阻率超过500Ωcm，因此，不优选。另外，作为RE，更优选选择Sm、Gd、Er，作为TM，更优选选择Nb。进一步，更优选每次等量添加上述RE(Sm、Gd、Er)和TM(Nb)。通过设为上述供体种类和添加方法，从而常温电阻率减少效果进一步提高。
另外，在上述组成式中，m优选为0.950≤m≤1.050的范围。在m小于0.950时，半导体化变得不充分，常温电阻率超过500Ωcm，从而不优选。另外，如果m超过1.050，则烧结密度降低，耐受电压V0降低至小于400V/mm，因此，不优选。优选地，通过设为0.980≤m≤1.050的范围，从而常温电阻率减少效果进一步提高。
另外，对于上述组成式，作为副成分添加的Ca的成分范围相对于1mol的Ti位点(Ti和TM的总摩尔数)为0.001mol以上且0.055mol以下。在Ca的成分范围小于0.001mol时，半导体化变得不充分，常温电阻率超过500Ωcm。另外，如果Ca的成分范围超过0.055mol，则烧结密度降低，耐受电压V0降低。更优选地，通过设为0.01mol以上且0.04mol以下的范围，可以进一步减小常温电阻率。
具有这样的特征的半导体陶瓷组合物例如可以以如下的方式进行制造。
首先，作为起始原料，根据需要准备氧化铋(Bi2O3)、碳酸钠(Na2CO3)、氧化钛(TiO2)、碳酸钡(BaCO3)、碳酸钾(K2CO3)、碳酸钙(CaCO3)、氧化镧(La2O3)等的稀土类、氧化铌(Nb2O5)、氧化钽(Ta2O5)、氧化钒(V2O5)、碳酸锰(MnCO3)、氧化硅(SiO2)等的粉末，根据作为目标的组成进行称量。
另外，对于起始原料，除了氧化物以外，也可以使用如碳酸盐或者草酸盐那样的通过烧结成为氧化物的物质。
接着，将称量后的起始原料用球磨机在有机溶剂中或者纯水中充分混合5小时至20小时之后，进行充分地干燥。干燥温度例如为90℃左右。但是，在用干式混合进行上述起始原料的混合的情况下，也可以省略该干燥工序。
将这些干燥后的起始原料压制成型，制作煅烧用成型体，或者，在650℃～950℃下将粉末直接煅烧1小时～20小时左右。煅烧时的升温和降温速度一起设为例如50℃/小时～300℃/小时左右。本实施方式中的煅烧在大气中实施，不限定氧分压的高低。
用例如球磨机等在有机溶剂中或者水中将上述煅烧物充分粉碎5小时至20小时之后，进行充分干燥。干燥温度例如为90℃左右。
在该干燥后的煅烧物中加入有机粘合剂溶液(聚乙烯醇(Polyvinyl Alcohol：PVA))进行造粒。造粒之后，对该造粒粉进行单轴压制成型，制成圆柱、棱柱、圆板或矩形板。
优选可以在上述工序后追加实施冷等静压(Cold Isostatic Pressing：CIP)。此时，更优选在最大负荷压力98至343MPa下实施1～3分钟等静压。
对通过上述工序得到的成型体在400℃～800℃下进行热处理2小时～4小时左右，使粘合剂挥发，在950℃～1300℃下进行烧结2小时～4小时左右。烧结时的升温和降温速度一起设为例如50℃/小时～300℃/小时左右。本实施方式中的烧结在大气中实施，但不限定氧分压的高低。
另外，在氮气气氛中进行烧结的情况下，由于进一步需要在800～1000℃的氧化性气氛中进行热处理，因此，从工序简化的观点出发，优选在大气中进行烧结。
根据需要对得到的烧结体进行研磨，形成电极。电极除了涂布电极膏体进行烧结以外，也可以通过蒸镀或溅射成膜等来形成。
图1表示使用了本实施方式所涉及的半导体陶瓷组合物的PTC热敏电阻元件的一部分结构例。该PTC热敏电阻元件1具备由本申请发明的BaTiO3系半导体陶瓷组合物构成的陶瓷素体2和在陶瓷素体的相对的两个主面上形成的电极3a和3b。作为电极3a和3b，可以以由Cu、Ni、Al、Cr、Zn、Ag、Ni-Cr合金、Ni-Cu等的导电性材料构成的一层结构或多层结构形成。另外，图1所示的PTC热敏电阻1是圆板状，但也可以是长方体状等。另外，上述电极3a和3b可以通过镀覆、溅射、蒸镀、丝网印刷等来形成。这些电极3a和3b上可以通过例如没有图示的电线等与没有图示的外部电源电连接。
本实施方式所涉及的PTC热敏电阻例如可以以如下方式进行制作。首先，制作如上所述的半导体陶瓷组合物之后，根据需要加工成规定的大小，形成陶瓷素体2。接着，在该陶瓷素体2上通过例如蒸镀电极3a和3b，从而可以得到图1所示的PTC热敏电阻。
本实施方式所涉及的半导体陶瓷组合物可以用于例如加热器元件或过热检测元件等中，也可以适用于这些以外的元件中。
实施例
以下，基于实施例以及比较例来更具体地说明本发明，但是本发明没有被限定于以下的实施例。
[实施例1～73、比较例1～27]
作为起始原料准备BaCO3、TiO2、Bi2O3、Na2CO3、K2CO3、CaCO3、SiO2、MnCO3、RE的氧化物(例如Y2O3)和TM的氧化物(例如Nb2O5)，以烧结后的组成成为表1～9的方式称量各原料，然后，使用球磨机在乙醇中进行湿式混合，然后，进行干燥，在800℃下煅烧2小时。
将上述煅烧体使用球磨机在纯水中进行湿式粉碎之后，进行脱水干燥。对其使用PVA等粘合剂进行造粒，得到造粒粉体。通过单轴挤出机将其成型为圆柱状(直径17mm×厚度1.0mm)，在大气气氛下在1200℃下进行烧结2小时，得到烧结体。
在上述烧结体的两面通过丝网印刷涂布Ag-Zn膏体，在大气中在500～800℃下进行烧结形成电极之后，在25℃至280℃下测定电阻率的温度特性。另外，在环境温度为25℃下在电极间慢慢施加电压测定耐受电压(击穿电压)，将该值除以半导体陶瓷组合物的板厚(单位为mm)得到的值作为耐受电压V0(V/mm)。
另外，作为通电试验，施加20V的直流电压1000小时之后，在环境温度25℃下进行测定，求得试验前的电阻率ρ0和试验后的电阻率ρ1的差△ρ(＝ρ1-ρ0)，算出电阻变化率△ρ/ρ0。将结果示于表1～8中。
[实施例74]
除了将烧结时的气氛设定为氮气气氛，进一步在800℃的大气中进行热处理以外，与实施例1同样地制作半导体陶瓷组合物，进行与实施例1～73同样的评价。将结果示于表9中。
根据表1可知，Bi元素的成分范围x与居里点有关联。根据实施例1～5可知，如果Bi元素的成分范围为0.01≤x≤0.15，则居里点向高于BaTiO3的居里点即120℃的高温侧移动，并且常温电阻率为500Ωcm以下，耐受电压为400V/mm以上，电阻变化率△ρ/ρ0保持在20％以下。另外，可知x的含量越多，则居里点越向高温侧移动，常温电阻率倾向于稍微增加。Bi元素的成分范围小于0.01的比较例1中常温电阻率小，但居里点为120℃以下。另外，可知Bi的成分范围超过0.15的比较例2中常温电阻率大大超过500Ωcm。
[表1]
根据表2可知，可以得到良好的PTC特性的A的成分范围y与Bi元素的成分范围x有关联。另外，A同时包含Na和K元素。根据实施例1、3、5以及6～13可知，如果y的成分范围0<y≤0.30，则常温电阻率小，耐受电压为400V/mm以上，电阻变化率△ρ/ρ0保持在20％以下。另外，可知在x一定的情况下，y越多，则耐受电压越倾向于上升。另外，可知y的成分范围超过0.30的比较例4、6和8中耐受电压变高，但是常温电阻率大大超过500Ωcm。
[表2]
根据表3可知，Na和K的Na/(Na+K)的比低于0.1的比较例9中，常温电阻率超过500Ωcm，Na和K的Na/(Na+K)的比为1.00的比较例10中耐受电压没有变高。另外，可知Na、K的Na/(Na+K)的比越低，则居里温度和耐受电压变得越高。
[表3]
根据表4可知，通式(1)中Ba位点(v+w+x+y)相对于Ti位点(Ti和TM的总摩尔数)的比m与常温电阻率有关联。可知m的范围为0.950≤m≤1.050的实施例18、19和20中，常温电阻率小，耐受电压为400V/mm以上，电阻变化率△ρ/ρ0推移至20％以下。可知m小于0.950的比较例11中，常温电阻率超过500Ωcm，m超过1.050的比较例12中耐受电压为400V/mm以下。
[表4]
根据表5可知，作为副成分的Ca的成分范围与常温电阻率有关联。可知Ca的成分范围为0.001mol以上且0.055mol以下的实施例19、21和22中，常温电阻率小，耐受电压为400V/mm以上，电阻变化率△ρ/ρ0推移至20％以下。可知在Ca的成分范围小于0.001mol的比较例13中，常温电阻率增大；在Ca的成分范围超过0.055mol的比较例14中，耐受电压低于400V/mm。
[表5]
根据表6的实施例23～64可知，如果RE和TM的总量：(w+z)为0.01以下，则有常温电阻率减少效果。另外，可知对于(w+z)超过0.01的比较例15～27，常温电阻率超过500Ωcm。另外，根据实施例59～64可知，即使(w+z)为相同值，每次等量添加RE和TM时的常温电阻率小。
[表6]
根据表7的实施例19以及65～69可知，通过相对于1mol的Ti位点(Ti和TM的总摩尔数)(u+z)以元素换算为0.035mol以下的比例添加Si，从而有常温电阻率减少效果。
[表7]
根据表8的实施例19以及70～73可知，通过相对于1mol的Ti位点(Ti和TM的总摩尔数)以元素换算为0.0015mol以下的比例添加Mn，从而有PTC突跳的提高效果。
[表8]
根据表9的实施例19和74可知，将烧结时的气氛设定为氮气气氛(PO2＝10-7atm)的情况下，与在大气中烧结可以得到大致同等的特性。
[表9]

Claims (4)

1.一种半导体陶瓷组合物，其特征在于，
具备以下述通式(1)所表示的BaTiO3系化合物为主成分的烧结体，
(BavBixAyREw)m(TiuTMz)O3 (1)
上述通式(1)中，上述A同时包含Na和K这2种元素，上述RE为选自Y、La、Ce、Pr、Nd、Sm、Gd、Dy和Er中的至少1种元素，上述TM为选自V、Nb和Ta中的至少1种元素，w、x、y、z和m满足下述式(2)～(7)，
0.01≤x≤0.15 (2)
x≤y≤0.3 (3)
0≤(w+z)≤0.01 (4)
v+x+y+w＝1 (5)
u+z＝1 (6)
0.950≤m≤1.050 (7)
进一步，相对于1mol的Ti位点即Ti和TM的总摩尔数，以元素换算以0.001mol以上且0.055mol以下的比例含有Ca，并且Na/(Na+K)的比为0.1以上且小于1。
2.如权利要求1所述的半导体陶瓷组合物，其特征在于，
所述半导体陶瓷组合物进一步相对于1mol的Ti位点即Ti和TM的总摩尔数，以元素换算以0.035mol以下的比例含有Si。
3.如权利要求1或2所述的半导体陶瓷组合物，其特征在于，
所述半导体陶瓷组合物进一步相对于1mol的Ti位点即Ti和TM的总摩尔数，以元素换算以0.0015mol以下的比例含有Mn。
4.一种PTC热敏电阻，其中，
具备陶瓷素体和在所述陶瓷素体的表面上形成的电极，所述陶瓷素体使用权利要求1～3中任一项所述的半导体陶瓷组合物而形成。
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110352182A (zh) * 2018-02-08 2019-10-18 日本碍子株式会社 半导体制造装置用加热器
CN111090063A (zh) * 2018-10-24 2020-05-01 Tdk株式会社 磁传感器

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017143090A (ja) * 2016-02-08 2017-08-17 Tdk株式会社 半導体磁器組成物およびｐｔｃサーミスタ
CN107188555A (zh) * 2017-06-22 2017-09-22 广西大学 一种陶瓷靶材的制备方法
CN111056836A (zh) * 2019-12-30 2020-04-24 江苏钧瓷科技有限公司 一种高Tc低阻无铅PTC材料的制备方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1237265A (zh) * 1997-09-05 1999-12-01 Tdk株式会社 正特性半导体陶瓷的制造方法
CN101528632A (zh) * 2006-10-27 2009-09-09 日立金属株式会社 半导体陶瓷组合物及其制备方法
CN101528633A (zh) * 2006-11-01 2009-09-09 日立金属株式会社 半导体陶瓷组合物及其制备方法
CN101925968A (zh) * 2008-01-29 2010-12-22 株式会社村田制作所 芯片型半导体陶瓷电子元器件
CN104513061A (zh) * 2013-10-03 2015-04-15 Tdk株式会社 半导体陶瓷组合物以及ptc热敏电阻

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS56169301A (en) 1980-06-02 1981-12-26 Tohoku Metal Ind Ltd Method of producing barium titanate semiconductor porcelain
CN100335415C (zh) 2003-02-28 2007-09-05 新加坡纳米材料科技有限公司 一种制备各种晶态钙钛矿类化合物粉体的方法
WO2008038538A1 (fr) * 2006-09-28 2008-04-03 Murata Manufacturing Co., Ltd. Composition de porcelaine semiconductrice de titanate de baryum et dispositif ptc utilisant celle-ci
WO2010067868A1 (ja) 2008-12-12 2010-06-17 株式会社 村田製作所 半導体セラミック及び正特性サーミスタ
WO2010067867A1 (ja) 2008-12-12 2010-06-17 株式会社 村田製作所 半導体セラミック及び正特性サーミスタ
KR20120077401A (ko) * 2010-12-30 2012-07-10 삼성전자주식회사 유전체 세라믹 및 그 제조방법
JP2012209292A (ja) 2011-03-29 2012-10-25 Murata Mfg Co Ltd 正特性サーミスタ
WO2014141814A1 (ja) 2013-03-11 2014-09-18 Tdk株式会社 Ｐｔｃサーミスタ磁器組成物およびｐｔｃサーミスタ素子
JP5761540B2 (ja) 2013-06-28 2015-08-12 セイコーエプソン株式会社 圧電材料、圧電素子、液体噴射ヘッド、液体噴射装置、超音波センサー、圧電モーター及び発電装置

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1237265A (zh) * 1997-09-05 1999-12-01 Tdk株式会社 正特性半导体陶瓷的制造方法
CN101528632A (zh) * 2006-10-27 2009-09-09 日立金属株式会社 半导体陶瓷组合物及其制备方法
CN101528633A (zh) * 2006-11-01 2009-09-09 日立金属株式会社 半导体陶瓷组合物及其制备方法
CN101925968A (zh) * 2008-01-29 2010-12-22 株式会社村田制作所 芯片型半导体陶瓷电子元器件
CN104513061A (zh) * 2013-10-03 2015-04-15 Tdk株式会社 半导体陶瓷组合物以及ptc热敏电阻

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110352182A (zh) * 2018-02-08 2019-10-18 日本碍子株式会社 半导体制造装置用加热器
CN110352182B (zh) * 2018-02-08 2022-02-08 日本碍子株式会社 半导体制造装置用加热器
CN111090063A (zh) * 2018-10-24 2020-05-01 Tdk株式会社 磁传感器
CN111090063B (zh) * 2018-10-24 2023-01-17 Tdk株式会社 磁传感器

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