CN1172324C - 半导体陶瓷组合物和使用该组合物的半导体陶瓷元件 - Google Patents

半导体陶瓷组合物和使用该组合物的半导体陶瓷元件 Download PDF

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CN1172324C
CN1172324C CNB02106671XA CN02106671A CN1172324C CN 1172324 C CN1172324 C CN 1172324C CN B02106671X A CNB02106671X A CN B02106671XA CN 02106671 A CN02106671 A CN 02106671A CN 1172324 C CN1172324 C CN 1172324C
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oxide
mole
semiconductive ceramic
temperature
constant
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CN1397958A (zh
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中山晃庆
石川辉伸
新见秀明
����һ
浦原良一
坂部行雄
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Murata Manufacturing Co Ltd
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Abstract

公开了一种具有负电阻-温度特性的半导体陶瓷组合物，该组合物包括氧化钴镧作为主组分；选自Si、Zr、Hf、Ta、Sn、Sb、W、Mo、Te、Ce、Nb、Mn、Th和P元素的至少一种氧化物作为副组分；以及B的氧化物。该组合物的烧结密度高，由其制得的半导体陶瓷元件可用于防止骤增电流、用于延迟电动机启动，或者用于与温度补偿的晶体振荡器一起使用或用于温度补偿。

Description

半导体陶瓷组合物和使用该组合物的半导体陶瓷元件
本申请是申请日为1998年10月8日、发明名称为“半导体陶瓷组合物和使用该组合物的半导体陶瓷元件”的发明专利申请CN98120933.5的分案申请。
技术领域
本发明涉及半导体陶瓷组合物，特别是具有负电阻-温度特性的半导体陶瓷组合物。本发明还涉及使用该半导体陶瓷组合物(负温度系数＂NTC＂热敏电阻)的半导体陶瓷元件。该元件用于例如防止电流骤增和实现电动机的软启动。
背景技术
“热敏电阻”一词来源于“热敏感性电阻”，是指电阻随温度变化的元件。负温度系数热敏电阻(NTC热敏电阻)是一种半导体陶瓷元件，其特征是电阻随温度升高而下降。常数B用下式定义，其中ρ(T)是温度为T时的电阻率，ρ(To)是温度为To时的电阻率，ln是自然对数。
            常数B＝[lnρ(To)-lnρ(T)]/(1/To-1/T)
常数B越大，NTC热敏电阻的每单位温度变化的电阻变化也越大。
NTC热敏电阻包括例如在用于电子器件的电源整流电路中。该电源的整流电路具有大电容的滤波电容器。NTC热敏电阻抑制电源刚接通时强的骤增电流流入电容器中。此后，热敏电阻通过自加热作用而使电阻值变低，因此电路处在稳定的状态下工作。NTC热敏电阻能用来得到电路的软启动，并且用来保护大电容的整流器和电容器。
已经用含过渡金属元素的尖晶石复合氧化物作为NTC热敏电阻的材料。
对于用来防止骤增电流的理想NTC热敏电阻的一个要求是在高温(140-200℃)下热敏电阻的电阻值足够低。随着热敏电阻的阻值下降，在电路于稳定状态下工作时节省了电能。
为了降低热敏电阻在高温下的电阻值，高温下的常数B要增加。常规的NTC热敏电阻的常数B最多为3250K。
另一个要求是热敏电阻在低温下(在-10℃至+60℃的范围内)的电阻值不必非常高。可发现常规NTC热敏电阻的电阻值增加相当大，尤其是在低于0℃的低温下。结果，低温下发生的电压降有时会妨碍电子器件的正常启动。为了防止低温下电阻的增加，要降低低温下的常数B。
据报道，氧化钴镧(lanthanum cobalt oxide)的常数B与温度有关(例如见V.G.Bhide和D.S.Rajoria的Phys.Rev.B6，[3]，1072，1972，等)。
本发明人早就得到了一种NTC热敏电阻，它能满足上述两个要求，即在室温附近常数B为3000K或更小，在高温下常数B为4000K或更大，这可以通过向由氧化钴镧形成的主要组分中混入选自Si、Zr、Hf、Ta、Sn、Sb、W、Mo、Te和Ce的至少一种元素来完成(日本专利申请公开号7-176406)。所得的NTC热敏电阻的电阻率和常数B与添加剂的用量成正比。这是因为添加剂在氧化钴镧中用作施主以补偿氧化物中所含杂质(受主，如Ni、Ca等)的电荷。因此，如果添加剂过量混入，那么电阻率和常数B在室温下会变低。
氧化钴镧的电阻率和常数B在室温(25℃-140℃)下的峰值约为20Ω·cm和约4700K。通常得不到电阻率等于或大于上述值的NTC热敏电阻。
随着NTC热敏电阻的应用，需要电阻率等于或大于上述值的电阻。虽然可以通过增加NTC热敏电阻的容量来得到较高的电阻率，但是增加容量与减小元件的要求是相悖的。根据热敏电阻的类型对其容量进行改进会导致生产成本的增加。
同时，氧化钴镧的烧结能力非常差，它的烧结密度有时不能达到90％或更高的理论密度。迄今为止，常规的烧结助剂(如SiO2)对其不起作用，因为施主和受主(以非常少量存在)之间的平衡影响了电阻-温度特性。
发明内容
因此，本发明的一个目的是提供一种半导体陶瓷组合物，它在室温范围内的电阻率高于常规组合物在该范围内的电阻率。
本发明的另一个目的是增强所述组合物的烧结能力。
根据本发明，提供了一种具有负电阻-温度特性的半导体陶瓷组合物，其中该组合物包括氧化钴镧作为主组分，以及选自Fe和Al元素的至少一种氧化物和选自Si、Zr、Hf、Ta、Sn、Sb、W、Mo、Te、Ce、Nb、Mn、Th和P元素的至少一种氧化物作为副组分。
较好的是选自Fe和Al元素的至少一种氧化物的总含量换算成元素，为0.001-30％(摩尔)，选自Si、Zr、Hf、Ta、Sn、Sb、W、Mo、Te、Ce、Nb、Mn、Th和P元素的至少一种氧化物的总含量换算成元素，为0.001-10％(摩尔)。
此外更好的是，选自Fe和Al元素的至少一种氧化物的总含量换算成元素，为0.1-10％(摩尔)，选自Si、Zr、Hf、Ta、Sn、Sb、W、Mo、Te、Ce、Nb、Mn、Th和P元素的至少一种氧化物的总含量换算成元素，为0.1-5％(摩尔)。
上述氧化钴镧可以的形式为LaxCoO3(0.60≤x≤0.99)。
上述LaxCoO3中的La可以用Pr、Nd和Sm中的任一种元素部分取代。
可以将B的氧化物加入一种具有负电阻-温度特性的陶瓷中，该陶瓷包括：
氧化钴镧作为主组分；
选自Si、Zr、Hf、Ta、Sn、Sb、W、Mo、Te、Ce、Nb、Mn、Th和P元素的至少一种氧化物作为副组分。
加入B的氧化物能增加烧结密度。
这些组合物可用于制造NTC热敏电阻，它能用来防止电流骤增或者用来控制电动机以得到软启动。
附图说明
图1是本发明NTC热敏电阻的部分剖面图。
具体实施方式
以下通过实施例说明本发明的实施方案。
实施例1
本实施例是使用La0.94CoO3作为氧化钴镧的实施方案。
首先，称量并混合LaxCoO3和Co3O4的粉末，以将镧与钴的摩尔比调节至0.94。接着对表1和2中所示的每种添加元素以化合物(如氧化物)形式称取预定量，混入经称重的粉末混合物。表1和2中所示添加元素的量是换算成元素的量。
将每种如此得到的粉末边加入纯水，边使用尼龙球的球磨湿式混合16小时，然后干燥。所得混合物于1000℃下煅烧2小时。研磨经煅烧的材料，向其中加入3％(重量)的醋酸乙烯酯粘合剂，然后边加入纯水，边使用尼龙球的球磨再湿式混合16小时。此后，将混合物干燥、粒化、压制成盘状，在空气中于1350℃下煅烧2小时，由此得到半导体陶瓷1。然后，将铂糊(platinum paste)丝网印刷在该半导体陶瓷的两表面上，半导体陶瓷在空气中于1000℃下焙烧2小时，形成外部电极2和3，从而得到NTC热敏电阻4(如图1)。半导体陶瓷的表面也可任选地用树脂层5涂覆以保护半导体陶瓷。也可以得到具有另一种结构的NTC热敏电阻，如内含多层电极的NTC热敏电阻。
测量如此得到的NTC热敏电阻的电阻率ρ和常数B这些电特性。结果见表1和2。在表1和2中，以＂*＂标记的样品编号表示处于本发明范围之外的热敏电阻，其它的则是在本发明范围内的热敏电阻。电阻率ρ是在25℃时测得的。
根据方程式(1)，此处得到的常数B，即B(-10℃)和B(140℃)如下定义：
B(-10℃)＝[lnρ(-10℃)-lnρ(25℃)]/[1/(-10+273.15)-1/(25+273.15)]
B(140℃)＝[lnρ(140℃)-lnρ(25℃)]/[1/(140+273.15)-1/(25+273.15)]
随着常数B(-10℃)下降，由外部温度变化感应引起的电阻值的波动范围下降，较低温度时，电阻值之上升受到了抑制。因此，前述较低温度时电压的下降问题得到了克服。
随着常数B(140℃)增加，电阻率随温度增加而激烈下降。因此，配备有NTC热敏电阻的电路一经启动，大电流就被抑制了，此后电路处在稳定状态下工作，电能损耗被抑制在低水平。具有这些特性的NTC热敏电阻特别适宜在电路中用于抑制骤增电流的元件，如在电源接通工作期间存在的元件，或是有大电流流经的类似元件。
                                        表1
  样品编号        添加元素       添加元素   电阻率ρ25℃(Ω·cm)             常数B
   种类     量(摩尔％)    种类     量(摩尔％)   B(-10℃)(K)   B(140℃)(K)
*1-1 Zr 1 Fe 0 19.8 2620 4730
  1-2     Zr     1     Fe     0.0005     19.8     2630     4730
  1-3     Zr     1     Fe     0.001     22.6     2610     4720
  1-4     Zr     1     Fe     0.01     24.9     2680     4730
  1-5     Zr     1     Fe     0.1     26.2     2650     4720
  1-6     Zr     1     Fe     1     28.6     2630     4720
  1-7     Zr     1     Fe     10     50.3     2670     4730
  1-8     Zr     1     Fe     20     76.1     2650     4720
  1-9     Zr     1     Fe     30     99.4     2640     4730
  1-10     Zr     1     Fe     40     139.7     2970     4210
  *1-11     Zr     0     Fe     5     9.4     520     1580
  1-12     Zr     0.0005     Fe     5     13.1     900     2510
  1-13     Si     0.001     Fe     5     19.8     1930     4250
  1-14     Mo     0.05     Fe     5     19.8     1820     4580
  1-15     Sn     0.5     Fe     5     22.6     2410     4680
  1-16     Sb     1     Fe     5     24.9     1970     4460
  1-17     Te     1     Fe     5     26.2     2630     4530
  1-18     Hf     5     Fe     5     19.6     2260     4310
  1-19     Ta     5     Fe     5     18.9     2100     4320
  1-20     W     10     Fe     5     15.4     2000     4120
  1-21     Ce     10     Fe     5     16.1     2090     4200
  1-22     Zr     20     Fe     5     12.4     800     1790
                                            表2
  样品编号       添加元素       添加元素   电阻率ρ25℃(Ω·cm)           常数B
   种类     量(摩尔％)    种类     量(摩尔％)   B(-10℃)(K)   B(140℃)(K)
1-23 Zr 1     FeAl     0.50.5 28.6 2630 4720
1-24 Si 1     FeAl     15 27.3 2570 4550
1-25 Mo 0.5     FeAl     55 50.3 2810 4430
1-26 W 0.5     FeAl     510 62.4 2850 4410
1-27     ZrCe     0.505     FeAl     155 72.0 2730 4500
1-28     WCe     0.051     FeAl     105 67.9 2590 4620
由表1和2可见，在含有La0.94CoO3作为主组分，以及选自Fe和Al元素的至少一种氧化物和选自Si、Zr、Hf、Ta、Sn、Sb、W、Mo、Te和Ce元素的至少一种氧化物作为副组分的半导体陶瓷组合物中，得到了负电阻-温度特性，电阻率ρ在室温下范围较宽，同时常数B在-10℃和140℃时的波动被限制在一定的范围内。
特别地，如果选自Fe和Al元素的至少一种氧化物的含量换算成元素，为0.001％(摩尔)或更多时，能够得到添加元素的显著效果，得到室温下增加的电阻率。此外，如果含量为30％(摩尔)或更低，则室温下的电阻率会降至100Ω·cm以下，常数B在高温下保持高值，较好的是使得电阻值在高温下有足够的下降。
尤其是如果选自Fe和Al元素的至少一种氧化物的总含量换算成元素，为0.001-30％(摩尔)，并且选自Si、Zr、Hf、Ta、Sn、Sb、W、Mo、Te和Ce元素的至少一种氧化物的总含量换算成元素，为0.001-10％(摩尔)时，可以得到优良的结果：B(-10℃)为1820-2850K，B(140℃)为4120-4730K，ρ(25℃)为15.4-99.4Ω·cm。
此外，如果选自Fe和Al元素的至少一种氧化物的总含量换算成元素，为0.01-10％(摩尔)，并且选自Si、Zr、Hf、Ta、Sn、Sb、W、Mo、Te和Ce元素的至少一种氧化物的总含量换算成元素，为0.1-5％(摩尔)时，B(-10℃)为1970-2810K，B(140℃)为4310-4730K，ρ(25℃)为18.9-50.3Ω·cm。由此得到常数B的变化被进一步限制的半导体陶瓷组合物，尽管电阻率ρ的波动范围变窄了。
此外，通过使用由LaxCoO3表示的组合物作为氧化钴镧，也可以得到与本实施例中所得相同的效果。
特别是使用LaxCoO3(其中，0.60≤x≤0.99)时，常数B在高温下增至3000K或更高，由此显著地降低了升高温度时的电阻。
而且，使用Nb、Mn、Th或P来代替以上实施例中所用的Si、Zr、Hf、Ta、Sn、Sb、W、Mo、Te或Ce，也可以得到相同的效果。
实施例2
La0.85Pr0.09CoO3可以用作氧化钴镧。
首先，称量并混合La2O3、Pr6O11和Co3O4的粉末，以将La∶Co和Pr∶Co的摩尔比分别调节至0.85和0.09。接着称取预定量的化合物(如氧化物)，如表3所示的每种添加元素，混入经称重的粉末混合物。表3中所示的添加元素的量是换算成元素的量。
将每种如此得到的粉末边加入纯水，边使用尼龙球的球磨湿式混合16小时，然后干燥。所得的混合物于1000℃下煅烧2小时。煅烧后的材料，按实施例1中相同的方式处理，由此得到NTC热敏电阻。
用实施例1中相同的方式测量如此得到的NTC热敏电阻的电阻率ρ和常数B。
结果见表3。
                                        表3
    样品编号       添加元素        添加元素  电阻率ρ25℃(Ω·cm)           常数B
  种类     量(摩尔％)   种类 量(摩尔％)   B(-10℃)(K)   B(140℃)(K)
2-1 Zr 1     FeAl     0.50.5 29.1 2550 4620
2-2 Si 1     FeAl     15 27.0 2590 4440
2-3 Mo 0.5     FeAl     55 48.7 2630 4460
2-4 W 0.5     FeAl     510 65.0 2790 4450
2-5     ZrCe     0.50.5     FeAl     155 72.3 2740 4510
2-6     WCe     0.051     FeAl     105 65.7 2580 4560
由表3可见，在含有La0.85Pr0.09CoO3作为氧化钴镧的半导体陶瓷组合物中，与实施例1中所示La0.94CoO3的情况相同，得到了负电阻-温度特性，其电阻率ρ在室温下范围宽广，同时限制了常数B在-10℃和140℃时的波动。
实施例3
La0.85Nd0.09CoO3可以用作氧化钴镧。
首先，称量并混合La2O3、Nd2O3和Co3O4的粉末，以将La∶Co和Nd∶Co的摩尔比分别调节至0.85和0.09。接着称取预定量的化合物(如氧化物)，如表4所示的每种元素，混入经称重的粉末混合物。表4中所示的添加元素的量是换算成元素的量。
将每种如此得到的粉末边加入纯水，边使用尼龙球的球磨湿式混合16小时，然后干燥。所得混合物于1000℃下煅烧2小时。煅烧后的材料，按实施例1中相同的方式处理，由此得到NTC热敏电阻。
用实施例1中相同的方式测量如此得到的NTC热敏电阻的电阻率ρ和常数B。结果见表4。
                                       表4
    样品编号       添加元素       添加元素   电阻率ρ25℃(Ω·cm)          常数B
   种类     量(摩尔％)    种类     量(摩尔％)   B(-10℃)(K)   B(140℃)(K)
3-1 Zr 1     FeAl     0.50.5 28.5 2650 4700
3-2 Si 1     FeAl     15 24.9 2690 4560
3-3 Mo 0.5     FeAl     55 55.1 2830 4490
3-4 W 0.5     FeAl     510 60.0 2810 4500
3-5     ZrCe     0.50.5     FeAl     155 76.4 2700 4510
3-6     WCe     0.051     FeAl     105 66.0 2620 4630
由表4可见，在含有La0.85Nd0.09CoO3作为氧化钴镧的半导体陶瓷组合物中，与实施例1中所示La0.94CoO3的情况相同，得到了负电阻-温度特性，其电阻率ρ在室温下范围宽广，同时限制了常数B在-10℃和140℃时的波动。
实施例4
La0.85Sm0.09CoO3可以用作氧化钴镧。
首先，称量并混合La2O3、Sm2O3和Co3O4的粉末，以将La∶Co和Sm∶Co的摩尔比分别调节至0.85和0.09。接着称取预定量的化合物(如氧化物)，如表5所示的每种元素，混入经称重的粉末混合物。表5中所示的添加元素的量是换算成元素的量。
将每种如此得到的粉末边加入纯水，边使用尼龙球的球磨湿式混合16小时，然后干燥。所得混合物于1000℃下煅烧2小时。煅烧后的材料，按实施例1中相同的方式处理，由此得到NTC热敏电阻。
用实施例1中相同的方式测量如此得到的NTC热敏电阻的电阻率ρ和常数B.结果见表5。
                                            表5
    样品编号         添加元素        添加元素   电阻率ρ25℃(Ω·cm)         常数B
   种类     量(摩尔％)    种类     量(摩尔％)   B(-10℃)(K)   B(140℃)(K)
4-1 Zr 1     FeAl     0.50.5 25.0 2700 4650
4-2 Si 1     FeAl     15 24.3 2690 4690
4-3 Mo 0.5     FeAl     55 48.3 2600 4570
4-4 W 0.5     FeAl     510 58.0 2870 4510
4-5     ZrCe     0.50.5     FeAl     155 67.9 2620 4630
4-6     WCe     0.051     FeAl     105 65.1 2680 4540
由表5可见，在含有La0.85Sm0.09CoO3作为氧化钴镧的半导体陶瓷组合物中，与实施例1中所示La0.94CoO3的情况相同，得到了负电阻-温度特性，其电阻率ρ在室温下范围宽广，同时限制了常数B在-10℃和140℃时的波动。
在上述实施例1-4中，分别将La0.94CoO3、La0.85Pr0.09CoO3、La0.85Nd0.09CoO3和La0.85Sm0.09CoO3用作氧化钴镧，但是本发明并不限于此。被取代的La的量并不限于0.09。在用Eu、Y或类似元素部分取代La的氧化钴镧的情况下可以得到相同的结果。
以上描述清楚地表明，通过混合作为主组分的氧化钴镧和作为副组分的选自Fe和Al元素的至少一种氧化物和选自Si、Zr、Hf、Ta、Sn、Sb、W、Mo、Te、Ce、Nb、Mn、Th和P元素的至少一种氧化物，能得到具有负电阻-温度特性的半导体陶瓷组合物，其室温电阻率约为10Ω·cm至100Ω·cm的任意值，同时常数B保持在恒定水平。
因此，使用半导体陶瓷组合物能够制造具有负电阻-温度特性的半导体陶瓷元件(NTC热敏电阻元件)，它被应用于承受强的骤增电流的电路或需要强电流抑制的电路。
也就是说，如此制得的半导体陶瓷元件可以广泛用作延迟电动机启动、保护激光打印机的磁鼓、保护灯泡(如卤素灯)、以及消除器件或机器中所产生的骤增电流，它们在刚施加电压时即通过过量的电流，还消除接通电源操作时所产生的骤增电流，这些半导体陶瓷元件还可以用作温度补偿的晶体振荡器或用于温度补偿。然而，本发明并不限于这些用途。
实施例5
通过混入B，可以增加半导体陶瓷组合物的烧结密度。La0.94CoO3利用烧结特性可以用作氧化钴镧。
首先，称量并混合La2O3和Co3O4的粉末，以将La与Co的摩尔比调节至0.94。接着称取预定量的化合物(如氧化物)，如表6所示的每种元素，混入经称重的粉末混合物。表6中所示的添加元素的量是换算成元素的量。
将每种如此得到的粉末边加入纯水，边使用尼龙球的球磨湿式混合16小时，然后干燥。所得混合物于1000℃下煅烧2小时。研磨经煅烧的材料，向其中加入3％(重量)的醋酸乙烯酯粘合剂，然后边加入纯水，边使用尼龙球的球磨再湿式混合16小时。此后，将混合物干燥、粒化、压制成盘状，在空气中于1350℃下煅烧2小时，由此得到半导体陶瓷。然后，将铂糊丝网印刷在半导体陶瓷的两表面上，半导体陶瓷在空气中于1000℃下焙烧2小时，形成外部电极，从而得到NTC热敏电阻。
测量如此得到的NTC热敏电阻的电阻率和常数B这些电特性。结果见表6。在表6中，以＂*＂标记的样品编号表示处于本发明范围之外的热敏电阻，其它的是在本发明范围内的热敏电阻。
                                         表6
  样品编号        添加元素       添加元素   电阻率ρ25℃(Ω·cm)    常数BB(140℃)(K)    烧结密度(克/厘米2)
   种类      量(摩尔％)   种类     量(摩尔％)
  *1-1     Zr      0.5     B   0     12.5     4730      6.2
  1-2     Zr      0.5     B   0.00005     12.5     4720      6.2
  1-3     Zr      0.5     B   0.0001     12.6     4720      6.9
  1-4     Zr      0.5     B   0.001     12.4     4730      7.0
  1-5     Zr      0.5     B   0.01     12.5     4720      7.0
  1-6     Zr      0.5     B   0.1     12.5     4720      7.1
  1-7     Zr      0.5     B   1     12.6     4730      7.1
  1-8     Zr      0.5     B   5     12.6     4740      7.1
  1-9     Zr      0.5     B   10     14.5     4330      7.1
  1-10     Zr      0.5     B   20     17.6     4040      7.1
  *1-11     Zr      0     B   0.1     2.3     1920      7.1
  1-12     Zr      0.0005     B   0.1     5.3     3400      7.1
  1-13     Si      0.001     B   0.1     9.2     4520      7.1
  1-14     Mo      0.05     B   0.1     9.8     4570      7.1
  1-15     Sn      0.5     B   0.1     10.1     4620      7.1
  1-16     Sb      1     B   0.1     10.8     4650      7.1
  1-17     Te      1     B   0.1     10.7     4650      7.1
  1-18     Hf      5     B   0.1     12.1     4770      7.1
1-19 Ta 5 B 0.1 12.1 4740 7.1
  1-20     W      10     B   0.1     11.1     4630      7.1
  1-21     Ce      10     B   0.1     10.9     4610      7.1
  1-22     Zr      20     B   0.1     5.7     3600      7.1
由表6可见，在含有La0.94CoO3作为主组分，以及选自Si、Zr、Hf、Ta、Sn、Sb、W、Mo、Te和Ce元素的至少一种氧化物和B的氧化物半导体陶瓷组合物中，得到了烧结密度高的负电阻-温度特性材料，同时限制了室温时电阻率和140℃时常数B的波动。
如果B的含量换算成B，为0.0001％(摩尔)或更多，则能够得到添加元素的显著效果，使得烧结密度增加。此外，如果该含量为5％(摩尔)或更低，则高温下的电阻值会有足够的下降，同时常数B在高温下保持高值。
尤其是如果选自Si、Zr、Hf、Ta、Sn、Sb、W、Mo、Te和Ce元素的至少一种氧化物的总含量换算成元素，为0.001-10％(摩尔)，并且B的氧化物的含量为0.0001-5％(摩尔)时，烧结密度会有利地增加至6.9或更高，同时电阻率ρ(25℃)的波动被限制在9.2-12.6，常数B(140℃)被限制在4520-4740。
此外，通过使用由LaxCoO3表示的组合物作为氧化钴镧可以得到与本实施例所得相同的效果。特别是使用LaxCoO3(其中，0.60≤x≤0.99)时，常数B在高温下增至3000K或更高，由此足够地降低了升高温度时的电阻值。
此外，在用Pr、Nd、Sm、Eu、Y或类似元素部分取代La的氧化钴镧的情况下，可以得到相同的效果。
而且，使用Nb、Mn、Th或P的氧化物来代替Si、Zr、Hf、Ta、Sn、Sb、W、Mo、Te或Ce的氧化物，也可以得到与本实施例所得相同的效果。

Claims (3)

1.一种具有负电阻-温度特性的半导体陶瓷组合物，该组合物包括：
氧化钴镧作为主组分；
选自Si、Zr、Hf、Ta、Sn、Sb、W、Mo、Te、Ce、Nb、Mn、Th和P元素的至少一种氧化物作为副组分；以及
B的氧化物，
所述选自Si、Zr、Hf、Ta、Sn、Sb、W、Mo、Te、Ce、Nb、Mn、Th和P元素的至少一种氧化物的总含量换算成元素含量，为0.001-10摩尔％，B的氧化物的含量换算成元素B的含量，为0.0001-5摩尔％，
氧化钴镧的形式为LaxCoO3，其中0.60≤x≤0.99。
2.一种半导体陶瓷元件，它包括具有负电阻-温度特性的半导体陶瓷和至少一对连接在所述半导体陶瓷上的电极，所述陶瓷包括：
氧化钴镧作为主组分；
选自Si、Zr、Hf、Ta、Sn、Sb、W、Mo、Te、Ce、Nb、Mn、Th和P元素的至少一种氧化物作为副组分；以及
B的氧化物，
所述选自Si、Zr、Hf、Ta、Sn、Sb、W、Mo、Te、Ce、Nb、Mn、Th和P元素的至少一种氧化物的总含量换算成元素含量，为0.001-10摩尔％，B的氧化物的含量换算成元素B的含量，为0.0001-5摩尔％，
氧化钴镧的形式为LaxCoO3，其中0.60≤x≤0.99。
3.如权利要求2所述的半导体陶瓷元件，其特征在于它用于防止骤增电流、用于延迟电动机启动，或者用于与温度补偿的晶体振荡器一起使用或用于温度补偿。
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