CN1143255A - 具有正电阻温度系数的半导体陶瓷合成物及其制造方法 - Google Patents

具有正电阻温度系数的半导体陶瓷合成物及其制造方法 Download PDF

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CN1143255A
CN1143255A CN96105586A CN96105586A CN1143255A CN 1143255 A CN1143255 A CN 1143255A CN 96105586 A CN96105586 A CN 96105586A CN 96105586 A CN96105586 A CN 96105586A CN 1143255 A CN1143255 A CN 1143255A
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林康二
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Abstract

一种具有正电阻温度系数的半导体陶瓷合成物及其制造方法。该半导体陶瓷合成物包括含硅氧化物和锰的钛酸钡半导体陶瓷合成物，该半导体陶瓷合成物还包括以该钛酸钡半导体陶瓷合成物的量为基准含量为0.0005-0.02wt％的钠。

Description

具有正电阻温度系数的半导体 陶瓷合成物及其制造方法
本发明涉及具有正电阻温度系数的钛酸钡半导体陶瓷及其制造方法，尤其涉及一种含有硅氧化物和锰并具有正电阻温度系数的钛酸钡半导体陶瓷合成物及其制造方法。
钛酸钡半导体陶瓷合成物用作具有正电阻温度系数的半导体器件是大家熟知的。因为当温度超过居里点时，钛酸钡半导体陶瓷合成物的电阻会迅速增加，并且流过的电流会因此减小，所以它们具有各种不同的应用，如：电路的过流保护，电视接收器的布朗管的消磁等等。总之，在这些半导体器件应用于电路中时，因为在常温下它们的电阻值的巨大变化使电路的设计出现困难等等。因此，使电阻值的变化最小化是很必要的。
此外，通过向上述的钛酸钡半导体陶瓷合成物添加硅氧化物和锰来使高电压电阻和电阻-温度特性得到改善是已经为世人所公知的(JP-B-53-29386)。尽管含硅氧化物和锰的钛酸钡半导体陶瓷合成物的电特性很好，但仍需要准确控制煅烧温度和烧结温度才能使在常温下具有恒定电阻率的合成物稳定生产。(术语“JP-B”在这里表示经过审查的日本专利出版物。)
然而，控制煅烧温度和烧结温度不是很容易的，并且煅烧过的材料的电阻率是会随煅烧温度的变化而变化的，因此，必须通过控制烧结温度来调整最终半导体陶瓷合成物的电阻率，这样就引起了复杂的烧结温度控制的问题和工作效率低的问题。
鉴于此，本发明的一个目的就是提供一种具有正电阻温度系数的半导体陶瓷合成物及其制造方法，在本发明里最终半导体陶瓷合成物的电阻率可以不用改变烧结温度而通过调节所添加的钠含量的多少来控制，即使是对于随煅烧温度的起伏而改变电阻率的煅烧过的材料。
一种与本发明的情况相似的将钠加入其中的半导体陶瓷合成物在JP-A-4-311002中已公开，但它的目的是改善电阻温度系数，所以它在本发明目的和钠的添加量上明显不同于本发明(这里所用的术语“JP-A”指未经审查而公开的日本专利申请。)
第一方面，本发明涉及一种包括含有硅氧化物和锰的钛酸钡半导体陶瓷合成物的具有正电阻温度系数的半导体陶瓷合成物，这种半导体陶瓷合成物进一步还包括以钛酸钡半导体陶瓷合成物的量为基准的从0.0005-0.02wt％的钠含量(wt为重量比)。
第二方面，本发明还涉及制造具有正电阻温度系数的半导体陶瓷合成物的方法，该方法包括以下步骤：
煅烧含硅氧化物和锰的钛酸钡半导体陶瓷合成物的初始材料；
向煅烧过的合成物中添加钠化合物，使钠的含量为以钛酸钡半导体陶瓷合成物的量为基准的0.0005-0.02wt％；和
烧结这种合成物。
根据本发明的具有正电阻温度系数的半导体陶瓷合成物，钠化物是以100份钛酸钡半导体陶瓷合成物中钠成分为0.0005-0.02wt％的量来添加的，这样半导体陶瓷合成物的电阻率就很容易控制。
根据本发明的制造具有正电阻温度系数的半导体陶瓷合成物的方法，应用了一种附加的步骤，在该步骤中钠化合物以根据100份钛酸钡半导体陶瓷合成物中钠含量占0.0005-0.02wt％的量添加，这样具有恒定电阻率值的半导体陶瓷合成物就可以稳定地生产了。
换句话说，在保持作施主成分的半导电试剂(Y2O3，La2O3，Nb2O5或类似物)和作受主成分的锰(Mn)之间的半导电平衡的同时，在微量范围内添加钠使半导体陶瓷合成物的电阻率尽可能减小，同时还阻止了击穿电压的劣化。
下面将参照优选实施例(例子)对本发明进行详细描述，但本发明并不限于此。
例1
(1)将按照下述配方(1)准备的初始材料BaCO3，TiO2，SrCO3，Y2O3，SiO2和MnCO3的混合物球磨混合15小时，然后脱水和干燥。
(Ea0.796Sr0.2Y0.004)TiO3＋SiO2(0.4％)＋Mn(0.02％)(1)
在配方(1)中，SiO2和Mn的量以合成物(Ba0.796Sr0.2Y0.004)TiO3的量为基准用重量百分比表示的。
(2)将初始材料的混合物产物在1,100℃，1,150℃或1200℃的煅烧温度下进行煅烧以制备3种煅烧的材料。
(3)将氢氧化钠作为以0-0.03wt％的钠的比例添加到100份上述已被粗磨的煅烧材料中，又一次将混合物产物混合球磨15小时，然后干燥，此时要防止钠的漏失。用2wt％的丙烯酸有机粘合剂将如此获得的材料混合，并使混合物粒化，然后在2t/cm2的模塑压力下将它们模塑成一直径为14mm，厚为3mm的盘状物。
尽管本例中采用了一种丙烯酸有机粘合剂作为有机粘合剂，但本发明并不特别限于该粘合剂，使用聚乙烯醇作粘合剂也可取得相同的效果。
(4)将上述得到的盘状成型物在1350℃下进行2小时烧结，以制备24种具有不同煅烧温度和钠成分的半导体陶瓷合成物。
(5)在这样制得的半导体陶瓷合成物的两个主表面上无电涂覆镍(Ni)从而制得欧姆电极，之后，在欧姆电极的表面上涂覆和印刷银糊剂从而制成一个电极。
在25℃测量这样得到的共24件半导体陶瓷合成物的电阻率值和击穿电压，结果见表1。
                              表1
样品 煅烧温度(℃) 钠添加量(wt％) 电阻率(Ω·cm) 击穿电压(Vdc)
    1     1,100     不添加     90     801
    2     1,100     0.0002     90     810
    3     1,100     0.0005     80     800
    4     1,100     0.001     75     750
    5     1,100     0.005     45     648
    6     1,100     0.01     25     525
    7     1,100     0.02     30     510
    8     1,100     0.03     60     402
    9     1,150     不添加     170     969
    10     1,150     0.0002     170     969
    11     1,150     0.0005     150     945
    12     1,150     0.001     120     900
    13     1,150     0.005     80     800
    14     1,150     0.01     52     520
    15     1,150     0.02     60     702
    16     1,150     0.03     100     490
    17     1,200     不添加     360     1,188
    18     1,200     0.0002     360     1,224
    19     1,200     0.0005     320     1,216
    20     1,200     0.001     300     1,170
    21     1,200     0.005     160     940
    22     1,200     0.01     80     800
    23     1,200     0.02     85     799
    24     1,200     0.03     170     493
如表1所示，当添加0.0005wt％或更多的钠时，半导体陶瓷合成物的电阻率值随钠的添加量的增加而减小，在每个煅烧温度(1100℃，1150℃，1200℃)下的电阻率值的变化变得很小。另外，击穿电压随Na添加量的增加趋于减小。
因而，不用改变烧结温度，而是当煅烧温度低时采用不添加或少量添加钠，或当煅烧温度高时采用增加钠添加量进行烧结的方法，这样就可稳定生产出具有较小变化的电阻率值的半导体陶瓷合成物。
例如，在初步焙烧的温度为1100℃，不添加钠(1号样品)的情况下，烧结后电阻率值为90Ω·cm，这个值与经过1200°煅烧，并添加了0.02wt％的钠烧结后(23号样品)的85Ω·cm的电阻率值几乎是相同的。
当将上述半导体陶瓷合成物作为电路中的半导体器件用作加热、限流等时，一般需要500Vdc的或更高的击穿电压。当添加0.03wt％或更多的钠时，将使烧结后的晶体结构劣化、击穿电压降低，这样就得不到令人满意的所要求的击穿电压。
因而添加含钠为0.0005-0.02wt％的钠化合物才是合乎需要的。如果钠含量低于0.0005wt％，是不会获得对电阻率的充分控制效果的。
例2
除应用了根据以下配方(2)准备的初始材料BaCO3，TiO2，PbO，Y2O3，SiO2和MnCO3的混合物外，重复例1的方法，可以得到共21件半导体陶瓷合成物样品。
(Ba0.847Pb0.15Y0.003)TiO3＋SiO2(0.8％)＋Mn(0.01％)(2)
在配方(2)中，SiO2和Mn的量是以合成物((Ba0.847Pb0.15Y0.003)TiO3的量为基准用重量百分比来表示的。
在25℃测量这样得到的21件半导体陶瓷合成物样品的电阻率值和击穿电压值，结果如表2所示。
                        表2
样品 煅烧温度(℃) 钠添加量(wt％) 电阻率(Ω·cm) 击穿电压(Vdc)
    1     1,050     不添加     120     504
    2     1,050     0.0003     120     504
    3     1,050     0.0005     110     528
    4     1,050     0.001     100     541
    5     1,050     0.01     70     518
    6     1,050     0.02     80     512
    7     1,050     0.03     300     480
    8     1,100     不添加     250     600
    9     1,100     0.0003     250     625
    10     1,100     0.0005     230     598
    11     1,100     0.001     220     594
    12     1,100     0.01     95     560
    13     1,100     0.02     110     550
    14     1,100     0.03     400     490
    15     1,150     不添加     400     800
    16     1,150     0.0003     400     800
    17     1,150     0.0005     360     864
    18     1,150     0.001     320     800
    19     1,150     0.01     120     576
    20     1,150     0.02     130     530
    21     1,150     0.03     500     475
与例1的情况类似，表2的结果表示出，当添加0.0005-0.02wt％的钠时，半导体陶瓷合成物的电阻率随钠添加量的增加而减小，在各个烧结温度(1050℃，1100℃，1150℃)下的电阻率值的变化变得很小。另外，击穿电压也随钠添加量的增加而减小，这与例1也是类似的。
因而，当添加钠含量为0.0005-0.02wt％的钠化合物时，可以得到与例1类似的效果。
在本发明中，以钛酸钡半导体陶瓷合成物的量为基准钠含量为0.0005-0.02wt％。优选的钠添加量为0.001到0.02wt％，最好是从0.001到0.008wt％。
尽管在例1和例2中钠的化合物采用了氢氧化钠，但本发明所用的钠化合物并不是特别限定的，采用其它如碳酸钠此类的钠化合物也可以得到同样的效果。在工业化规模生产中，从它的加工处理立场出发最好采用碳酸钠。
关于钛酸钡半导体陶瓷合成物的材料可采用各种钛酸钡材料，例如：那些其中的部分Ba由Sr、Pb、Ca此类的元素替代的材料；那些其中可包含Ya、La此类稀土元素或其它如Nb、Sb此类的元素作为导体材料的材料，和其中可添加SiO2、Al2O3、K2O、ZnO、P2O5、Fe此类物质作为添加剂的材料。一般来说，Ti含量为0.995-1.03mol，Pb含量为0-0.6mol，Ca含量为0-0.4mol，Ba含量为0.4-0.999mol Sr含量为0-0.6mol，Y含量为0.001-0.008mol。钛酸钡合成物一般含有0.2-1.0wt％的硅氧化物和0.002-0.04wt％的锰。
在根据本发明制造具有正电阻系数的半导体陶瓷合成物的过程中，用来制备陶瓷合成物的初始材料，煅烧温度和烧结温度都不是特别限定的。一般煅烧温度为1050-1250℃，烧结温度为1250-1400℃，它们是根据合成物的类型而定的。
因为本发明具有上述的组成，因此可以稳定地生产具有恒定电阻率值的半导体陶瓷合成物。
本发明具有下列效果：
(1)由于不同的煅烧温度引起所煅烧的材料的电阻率值变化，可以不用改变烧结温度，而是通过调节添加的钠化合物的量来修正。
(2)由于烧结温度的变化而引起的最终半导体陶瓷合成物的电阻率值的变化能够由钠化合物的添加来防止。
尽管上面参照特殊例子对本发明进行了详细描述，但在不脱离本发明的精神和范围的情况下各种改变和修正，对于本领域的技术人员来说都是显而易见的。

Claims (6)

1.一种具有正电阻温度系数的半导体陶瓷合成物，包括含硅氧化物和锰的钛酸钡半导体陶瓷合成物，所说半导体陶瓷合成物还包括以所说钛酸钡半导体陶瓷合成物的量为基准含量为0.0005-0.02wt％的钠。
2.根据权利要求1所述的一种半导体陶瓷合成物，其特征是所说半导体陶瓷合成物还包括以所说钛酸钡半导体陶瓷合成物的量为基准含量为0.001-0.02wt％的钠。
3.根据权利要求2所述的一种半导体陶瓷合成物，其特征是所说半导体陶瓷合成物还包括以所说钛酸钡半导体陶瓷合成物的量为基准含量为0.001-0.008wt％的钠。
4.一种制造具有正电阻温度系数的半导体陶瓷合成物的方法，所说方法包括以下步骤：
煅烧含硅氧化物和锰的钛酸钡半导体合成物的初始材料；
以所说钛酸钡半导体陶瓷合成物的量为基准以钠含量为0.0005-0.02wt％的比例向所说煅烧过的合成物中添加钠化合物；和烧结所说合成物。
5.根据权利要求4所述的一种制造半导体陶瓷合成物的方法，其特征是以所说钛酸钡半导体陶瓷合成物的量为基准，以钠含量为0.001-0.02wt％的比例向所说煅烧过的合成物中添加钠化合物。
6.根据权利要求5所述的一种制造半导体陶瓷合成物的方法，其特征是以所说钛酸钡半导体陶瓷合成物的量为基准，以钠含量为0.001-0.008wt％的比例向所说煅烧过的合成物中添加钠化合物。
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CN102976747A (zh) * 2012-12-04 2013-03-20 广西新未来信息产业股份有限公司 掺杂铌酸锂的钛酸钡基正温度系数电阻材料及其制备方法
CN115108827A (zh) * 2021-03-17 2022-09-27 华中科技大学 一种正温度系数热敏电阻及其制备方法
CN115108827B (zh) * 2021-03-17 2023-07-04 华中科技大学 一种正温度系数热敏电阻及其制备方法

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