CN1217087A - 单片多层压电驱动器及其制造方法 - Google Patents

单片多层压电驱动器及其制造方法 Download PDF

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CN1217087A
CN1217087A CN97194309A CN97194309A CN1217087A CN 1217087 A CN1217087 A CN 1217087A CN 97194309 A CN97194309 A CN 97194309A CN 97194309 A CN97194309 A CN 97194309A CN 1217087 A CN1217087 A CN 1217087A
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electrode layer
sintering
piezoelectric
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bed thickness
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CN1174496C (zh
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D·克拉梅
H·赫勒布兰德
K·鲁比茨
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Abstract

本发明涉及一种单片的压电驱动器,它包括一种化学计量的PZT陶瓷,这种陶瓷具有低的A位掺杂、含银和钯的电极层,它在好的压电电气特性时具有改善的机械强度。制造方法不依赖于在陶瓷中的B位掺杂导致最佳的颗粒大小和最佳的压电电气特性,可能得到150℃内的高应用温度的多层压电驱动器。

Description

单片多层压电驱动器及其制造方法
一般压电驱动器包括若干个安排在一个堆(Stapel)中的压电元件。每一个这样的元件包括一个压电陶瓷层，该层两面都具有一个金属电极。如果在这些电极上施加一个电压，那么随着晶格畸变激活压电陶瓷层，这个畸变沿着主轴导致一个长度膨胀。因为这些将小于沿主轴的层厚的千分之二，因此为了实现预期的绝对长度膨胀，必须预定一个活动压电陶瓷的一个相应较高的厚度。在一个压电元件范围内随着压电陶瓷厚度增加，启动压电元件所必需的电压也随之增高。为了将这些电压保持在可利用的极限内，在多层驱动器中压电元件的厚度一般在20到200μm之间。一个压电驱动器对于一个预期的长度膨胀因此必须具有相应数量的单独元件或者单独层。
在多层方法中已经公开的压电驱动器最多包括数百个单独层。可以将这些层安排在一个堆中，并例如粘合在一起。在US-5438232中公开了一个方法，该方法通过使用树脂粘合单独驱动器的方法制造多层驱动器。然而一个这样被粘合的堆对于很多应用只有一个太小的固定性，特别当必须使用压电驱动器传输大力时。一个单片的多层的压电驱动器具有足够高的固定性。为了制造这种压电驱动器，用电极金属替换压电陶瓷基膜安排在一个堆中并且一般被烧结在一起。那么仅能在堆中实现单独层足够的固定连接。在H.Moilanen et al的文章中，在杂志《传感器与驱动器A》,43(1994)357至365页中，公开了一种制造多层压电驱动器的方法，其中不仅通过交替的重叠相印产生陶瓷层而且还产生电极层。在一般间隔内，这时必需直到750度的干燥或者预烧结。
在S.Takahashi et al的文章，在《铁氧体电子》，1983，第90卷，181至190页中公开了制造多层驱动器的方法，多层驱动器通过重叠堆和胶合使用电极层印刷的陶瓷基膜并且接着烧结堆来实现。
在制造单片的多层压电陶瓷驱动器时，当设置处理条件时，特别当烧结处理时，不仅必须考虑压电陶瓷的材料特性而且必须考虑电极材料的材料特性。例如问题是优化压电陶瓷的烧结温度，压电陶瓷为了依赖于压电陶瓷的成分实现最佳颗粒大小并且因此优化压电电气性能，它可以位于1250度以上。在这样高的烧结温度下，只有铂可以作为电极材料。这说明陶瓷的一个弱交换作用，并且能和大部分压电陶瓷材料共同使用。缺点是铂材料费用高，以及在电极和压电陶瓷之间界面上的有限的强度。
如果使用性能价格比好的材料作为电极材料并且当多层电容器时一般使用Ag/Pd，那么由于合金的熔点限制烧结温度，例如合金的熔点可能低于1130℃(当Ag/Pd70/30)。因此人们受到压电陶瓷材料范围的限制，它的最佳烧结温度最大位于合金熔点上。这样的压电陶瓷为了降低最佳烧结温度包括对压电跃变基本材料(PZT)典型20％至50％B位掺杂。缺点是必需容忍在这种陶瓷中的一个被降低的居里温度，这限制了压电驱动器的最大温度。此外，在这种材料组合中，说明在压电陶瓷/电极的界面上的堆中强度受限制。
本发明的任务是给出一个以单片多层结构方式制造一个压电驱动器的方法，这种压电陶瓷不受具有较低的居里温度和应用温度的压电陶瓷材料的限制，这种压电陶瓷仍然具有好的压电特性并且此外这种压电陶瓷还具有一个高的机械连接强度。
这种任务根据本发明使用根据权利要求1的方法来解决。在从属权利要求中给出本发明特别的设计。
通过本发明，首先制造一个压电驱动器，这种压电驱动器不依赖于在一个具有一个含银/钯的电极层B位上的相反掺杂，在压电陶瓷层中具有最佳的颗粒大小。压电驱动器具有一个最佳值，从一个在最佳条件下并且从电极层分离的烧结的相同成分的压电陶瓷层来判断和估计。这时压电驱动器具有一个单片结构，其中压电陶瓷基膜和电极层一起被烧结并且因此在电极层和陶瓷层之间的连接中具有高强度。例如由银/钯合金构成的电极层在烧结处理中保持完好，因为这种处理在电极材料的熔化温度的下面进行。特别让人惊奇的是使用这种方法还可以实现一个压电驱动器，这种驱动器在堆中当单独层连接强度同时高时将一个低的或者完全的缺少的B位掺杂、性能价格比好的银/钯电极层、高的颗粒大小和好的压电电气特性结合在一起。使用这种方法，可以特别实现压电驱动器，这种压电驱动器具有一个高的居里温度，这能使压电驱动器在较高的使用温度下使用。现在这还没有公开，因为具有高居里温度的压电陶瓷可能比具有目前已使用电极层的低的熔点的压电陶瓷要求较高的烧结温度。如果最佳的烧结条件当烧结温度太低时不妨碍晶粒生长并且得出具有弱化压电电气特性的压电陶瓷。相反的得出好的压电电气特性，如果象根据本发明的压电陶瓷中一样压电陶瓷层的颗粒大小位于2至10μm的相同范围内，在陶瓷烧结中它是单独的也就是说没有电极使用较高的最佳烧结温度来实现。
同样根据本发明制造压电驱动器，从一个已经公开的制造单片多层元件的方法出发，其中提供的陶瓷基膜和电极材料交替重叠堆放并且接下来烧结在一起。根据本发明从类型为压电跃变基本材料(PZT)的一个压电陶瓷粉末出发，这种PZT具有一个化学计量的成分。补充这种化学计量成分，添加高度为1至5mol％的异价A掺杂材料的微小部分以及附加的1至5mol％铅氧化物的另外剩余量。此外使用含银和钯的电极材料。接下来胶合堆并且在受控条件下在氧化气体中烧结堆，其中烧结温度允许最大达到含银和钯的电极材料的熔点。如下执行烧结：蒸发化学计量的铅氧化物的剩余量并且此外银从电极层扩散到压电陶瓷层，其中达到化学计量的压电陶瓷成分。
本发明源自令人惊奇的认识：一个超化学计量的A位掺杂可以例如通过较高价的稀有金属在烧结处理期间通过从电极层出发的银扩散来补偿。为此的前提条件是：这时在氧化铅上同时存在着一个化学计量的剩余量。作为对此的说明，假设在烧结处理期间剩余的氧化铅在构成的压电陶瓷结构范围内产生流体状态，该状态支持银扩散。另外惊奇的是银的扩散处理是准自动调节的。扩散处理的动力是异价错误填充在PZT晶格中A位，PZT晶格通过一价的银来补偿。在实现化学计量的成分时，失去动力，因此停止银的继续扩散。另外本方法令人惊奇的是尽管对于一个70/30银/钯合金最大的烧结温度例如1130℃，但在压电陶瓷中达到高颗粒大小。假设在压电陶瓷中嵌入银的方法支持晶粒生长。尽管一个降低150℃到200℃的烧结温度，仍达到这样高的颗粒大小和高的压电电气值，像在一个最佳条件下的并且没有电极的烧结的元件一样，其中可以选择较高的烧结温度。实现至少96％的最佳密度还继续向低的温度偏移。
通过在压电陶瓷粉末中调节氧化铅剩余量实现另外的一个优选的结果。在压电陶瓷/电极层的界面上通过扩散钯构成一个含Pd-Pb-O的状态，该状态在烧结后在界面范围内的颗粒边界间隔中可以被检测到。可以设想这个状态对堆中陶瓷和电极层之间固定的改进的附着负责。
在优选的方法中，在氧化的气体中进行烧结。如果达到最大的烧结温度，那么在这个最大的温度中稳定阶段保持30至120分钟。
优选的相互不依赖的调整铅的剩余量而且在1至3mol％调节剩余的A-位掺杂。对于A位掺杂选择一个稀有元素例如镧或者钕。
下面根据两个实施例和附属的三个附图进一步说明本发明。
图1烧结后一个交替的压电陶瓷/电极堆的截面图，
图2烧结后超过层厚度的一个压电陶瓷层含银量的标准曲线。
图3烧结后在电极层/压电陶瓷层界面附近的范围的横界面。
1、使用330℃高的居里温度由压电陶瓷制造压电驱动器。
这里处理一个压电陶瓷粉，它具有一个标准成分Pb0.98Nd0.02(Zr0.54Ti0.46)O3.01。可以根据已经公开的方法制造尽可能均匀混合的原材料并且例如根据混合氧化方法或者使用化学的途径来表示，例如根据SolGel方法、Citrat方法、Oxalat方法或者通过所谓的金属有机物的初始化合物。在对于混合氧化方法，所有预先提供给陶瓷的阳离子以它们的氧化物的形式相互混合并且接下来在PZT中检查，而其他的制造方法从预期的阳离子的金属有机物的混合溶解出发。在所谓的Sol-Gel方法中通过溶解沉淀或者通过缓慢的加厚实现了在稍后的固体中阳离子的最终的均匀分配。
在煅烧之后重新磨细、调均匀，并且接下来使用一个有机胶合剂混合。然后使用如此实现的沉积物抽出或者得到基膜。接下来干燥基膜，提供了一个电极材料，例如使用一个印刷的糊，这种糊在一种具有总共可印刷的稠度的胶合剂中包括银/钯合金(70/30质量比)的颗粒。
压电陶瓷薄膜以下面的厚度制造，这种厚度在考虑烧结中的典型值为15％的线性损耗的情况下，得出20至200μm的压电陶瓷厚度。对于电极层，印刷电极材料，使电极层在烧结后具有大约2至3μm的电极层厚度。在小的层厚比例时，电极层/压电陶瓷层必须相应的印刷较多的电极材料，因此可以补偿导致电极材料损耗的银扩散的处理。这时电极层可以在全部面积上或者在一个任意的然而尽可能精炼的光栅印刷。
使用电极材料印刷的压电陶瓷基膜接下来相互重叠，其中得出压电陶瓷层和电极层的交替布局。通过在压力和提高的温度下的胶合处理预压缩堆，并且此后已经说明了足够的成分，因此它可能作为堆来使用。在这阶段，一个基面较大的堆在胶合后被分为若干个恒等的基面较小的堆，例如通过切割或者冲裁。若干个这样的部分堆可以再次联合成一个较大的堆。稍后的压电驱动器必需的层的总数视偏移的高度而定，上述偏移将通过设置电压使用压电驱动器来实现。因为一个单独的压电元件可以偏转的典型值为它厚度千分之一至千分之二，因此对于预期的总行程必需的单独层的数目能够完全简单的通过压电陶瓷层(在烧结后)的总共层厚来计算。为了预期的具有20μm总行程的应用例如厚度大约100μm的大约150个压电陶瓷单独层是足够的。
堆胶合后，在氧化的气体中当1130℃时被烧结。这个最高的温度保持大约1小时并且然后慢慢冷却。
图1实现了一种压电驱动器，它具有一个高的机械连接强度和一个高的机械承载能力。象通过堆的横截面所指出的，电极层1在它里面进一步结合。因此实现了较高的面积覆盖度，这种覆盖度在施加电压时可能有一个均匀的电场。压电陶瓷2具有一个2至10μm的颗粒。分析压电陶瓷得出下面的成分：Pb0.98Ag0.02Nd0.02(Zr0.54Ti0.46)O3。成分不仅是化学计量的而且在全部的压电陶瓷层上是均匀的。通过借助于微量分析的银浓度的测量得到验证。
图2说明依赖于到压电陶瓷层/电极层的距离说明银含量的横截面。指出了在全部的层厚度上银浓度最大限度的均匀分布。
图3说明了电极层/压电陶瓷层的界面范围的界面的放大图。为了容易识别，颗粒3是压电陶瓷层。到电极层1的基面上的晶界楔4，也就是几何的以陶瓷颗粒形式提供的中间空隙具有一个状态，在这个状态中，能够检查出钯、铅和氧。这个状态可能检查出从界面到电极层的距离在50nm到几μm的距离。假设电极层1借助于这个状态和压电陶瓷层2交替并且有助于它们根据本发明的提高的强度。在压电陶瓷层范围内或者在压电陶瓷颗粒3中的深处不能检查出钯。
这种成分的压电驱动器适合于大约150℃内的应用温度。
制造压电陶瓷层使用170℃低的居里温度。
根据已知的方法制造一个标准成分的压电陶瓷颗粒Pb0.99La0.01{Zr0.30Ti0.36(Ni1/3Nb2/3)0.34}O3.005。相应于第一个实施例，从中准备基膜，提供电极材料，堆叠成相应的堆，粘合并且当同样的条件下烧结。得到一个高强度的压电驱动器，对于压电驱动器，可以测定170℃的居里温度。因此这个驱动器可以在最大大约80℃的温度范围范围内使用。压电陶瓷层2在烧结后具有下面的化学计量成分：Pb0.98Ag0.01La0.01{Zr0.30Ti0.36(Ni1/3Nb2/3)0.34}O3。
这种压电陶瓷或者这种由其制造的多层结构的压电驱动器式中能看到的具有一个用于B位的复杂掺杂。因此得到具有改善压电电气特性的压电陶瓷，上述特性特别说明了一种被提高的相对的偏移。
对这些已经公开的特性改善的补充，作为根据本发明的特性，附加说明了这里在连接压电驱动器中改善的强度。这种陶瓷成分在烧结后还是化学计量的，因为在烧结期间通过银扩散补充剩余的(La)掺杂，通过从陶瓷中蒸发漏出剩余的铅氧化物。这里还得出在陶瓷层上相同的银含量，而钯再次仅在界面范围内，以在晶粒生长4中的第一个实施例中已经提到的含Pd-Pb-O的状态的形式被检测到。
使用本发明可能说明单片的多层结构的压电驱动器，这种压电驱动器与已经公开的压电驱动器相比具有一个改善的连接强度，它可以使用性能价格比好的含银/钯的电极层产生，并且它完全不依赖于可能存在的B位掺杂，在一个对其最佳的烧结温度下被烧结成具有好的压电电气特性的的一个高价值的陶瓷。因此它还特别可能制造多层压电驱动器，这种驱动器可在150℃的应用温度下工作，在动态工作时具有高机械承载能力和高可靠性。

Claims (5)

1．以单片多层结构的方法制造一个压电驱动器的方法，
-其中为了制造压电陶瓷基膜，从PZT类型的一个化学计量的压电陶瓷粉末出发，附加总共含量为1至5mol％的异价稀有金属的化学计量剩余量，并且附加1-5mol％的铅氧化物的化学计量剩余量，
-其中从含银和钯的糊中构成基膜电极层，
-其中相互重叠基膜并且接下来胶合，使在一个堆中，得到基膜和电极层的一个交替的序列，
-其中在控制烧结条件下如下烧结被胶合的堆：蒸发剩余的铅并且通过从电极层出发的银扩散补偿超化学计量的稀有金属掺杂，
-其中在1130℃的最大温度下在氧化气体中进行烧结，
-在烧结期间，稳定阶段在最高温度时保持30至120分钟，
-其中使用均匀的银掺杂实现化学计量的压电陶瓷层(2)。
2．根据权利要求1的方法，其中PbO的剩余量被调节在1至3mol％。
3．根据权利要求1或者2的方法，其中在实现电极层时，为了实现电极层(1)2-4μm的预期厚度(在烧结后)，选择一个较高的层厚作为层厚限度，稍后的层厚损失通过在陶瓷层中银扩散来补偿，并且确定层厚限度与压电陶瓷层/电极层的层厚比的比例，确定层厚限度与稀有金属的掺杂材料含量的比例。
4．根据权利要求1至3中任一个的方法，其中作为稀有金属，在化学计量的剩余量中La和Nd被附加到压电陶瓷粉末。
5．根据权利要求1至4中任一个的方法，其中使用一种压电陶瓷粉末，该粉末具有复杂的B位掺杂。
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ATE186613T1 (de) 1999-11-15
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CA2252392A1 (en) 1997-10-30
EP0894341A1 (de) 1999-02-03
EP0894341B1 (de) 1999-11-10
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JP2000508835A (ja) 2000-07-11
US6230378B1 (en) 2001-05-15
CN1174496C (zh) 2004-11-03
PT894341E (pt) 2000-04-28
CA2252392C (en) 2004-10-26
KR100450075B1 (ko) 2004-12-16
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