The property of ferroelectricity was first reported in 1921 in Rochelle salt (sodium potassium tartrate). Once considered a rare phenomenon limited to a comparatively small class of crystals, the discovery of ferroelectricity in the binary oxide compound barium titanate (BaTiO3) in the mid-1940s paved the way for rapid advances in the search of new materials. Since that time, a great many other ferroelectric compounds and solid solutions have been found and there has been broad interest in ferroelectric materials that has continued essentially uninterrupted until the present time. Ferroelectric materials remain subjects of intensive investigation today for three principal reasons. First, the unique dielectric, pyroelectric, piezoelectric, and electro-optic properties exhibited by ferroelectric crystals, ceramics, composites, and thin films can be exploited in great many devices of commercial importance. Second, apart from their many technological applications, ferroelectric materials as a class exhibit a great diversity of phase transitions that make them ideal objects for scientific investigations into the origins and mechanisms of a wide range of structural transformation phenomena. Finally, advances in thin-film deposition and nanoscale fabrication techniques made over the past two decades have created new possibilities for the integration of these materials into the ever expanding array of microelectronic devices. Ferroelectrics form a sub-group of functional (or smart) materials whose physical properties are sensitive to changes in external conditions such as temperature, pressure, and electric fields. Below some critical temperature TC, the dielectric displacement (electric polarization) spontaneously assumes non-zero values in the absence of any externally applied force. The transition between non-ferroelectric and ferroelectric phases is accompanied by a loss of symmetry, characterized by double-well minima below the transition temperature, resulting in a switchable polarization that is accompanied by a hysteresis in the electric field–dielectric displacement response. As a class of materials, ferroelectrics also exhibit unusually large and nonlinear generalized susceptibilities; their dielectric, piezoelectric, elastic, and other properties display critical behavior near the ferroelectric phase transformation temperature. Ferroelectrics may be regarded as high energydensity materials as well that can be configured to store, release or interconvert electrical and mechanical energy in a well-controlled manner. Their exceptionally large piezoelectric compliances, pyroelectric coefficients, and dielectric susceptibilities can be exploited in a variety of microelectronic devices. Important examples of these include piezoelectric sensors and actuators, pyroelectric thermal imaging devices, high-dielectric constant capacitors, electro-optic light valves, and thin-film memories. Because of their strongly non-linear dielectric response ferroelectrics can be utilized in applications such as frequency-agile phase shifters and filters in wireless telecommunications systems. Because the properties of ferroelectric materials that are exploited in technological applications are intimately S. P. Alpay (&) G. A. Rossetti Jr. Materials Science and Engineering Program, Departments of Chemical, Materials, and Biomolecular Engineering, University of Connecticut, Storrs, CT, USA e-mail: p.alpay@ims.uconn.edu
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