Lead-based relaxor dielectrics

Because of very high dielectric constants k > 20, 000), lead-based relaxor ferroelectrics, Pb(B, B2)02, where B is typically a low valence cation and B2 is a high valence cation, have been iavestigated for multilayer capacitor appHcations. Relaxor ferroelectrics are dielectric materials that display frequency dependent dielectric constant versus temperature behavior near the Curie transition. Dielectric properties result from the compositional disorder ia the B and B2 cation distribution and the associated dipolar and ferroelectric polarization mechanisms. Close control of the processiag conditions is requited for property optimization. Capacitor compositions are often based on lead magnesium niobate (PMN), Pb(Mg2 3Nb2 3)02, and lead ziac niobate (PZN), Pb(Zn 3Nb2 3)03. 

Relaxor ferroelectrics can be prepared either in polycrystalline form or as single crystals. They differ from the previously mentioned normal ferroelectrics in that they exhibit a broad phase transition from the paraelectric to ferroelectric state, a strong frequency dependence of the dielectric constant (i.e. dielectric relaxation) and a weak remanent polarization. Lead-based relaxor materials have complex disordered perovskite structures. 

More recently, because of their high dielectric constants k > 20 000), lead-based relaxor ferroelectrics have been used as capacitor materials. These ceramics have the general chemical formula Pb(5i, 2)03) vvhere Bi is typically a low-valence cation and B2 is a high-valence cation. Compositions used in capacitor applications are frequently based on lead magnesium niobate, Pb(Mgi/3,Nb2/3)03, and lead zinc niobate, Pb(Zni/3,Nb2/3)03. Other substituents and modifiers are added so that dielectric layers of these materials can be densified at relatively low temperatures ( 900 °C). The low firing temperatures permit the use of relatively inexpensive cofired electrode materials, such as silver. Typically, tape casting is used in the preparation of the dielectric layers. 

These lead-based materials (PZT, PLZT, PMN) form a class of ceramics with either important dielectric, relaxor, pie2oelectric, or electrooptic properties, and are thus used for appHcations ia actuator and sensor devices. Resistive properties of these materials ia film form mirror the conduction processes ia the bulk material. Common problems associated with their use are low dielectric breakdown, iacreased aging, and electrode iajection, decreasiag the resistivity and degrading the properties. 

In addition to the multilayered ceramic capacitors just described, many of the barium titanate-based compounds that exhibit high dielectric constants are used in single-layer tape-cast capacitor devices. Relaxor materials such as lead magnesium niobate (PMN), which are characterized by high dielectric constants, broad dielectric maxima, and low sintering temperatures, have been manufactured in thin sheets by tape casting. 

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