An overview of the state of art in ferroelectric thin films is presented. First, we review applications: microsystems' applications, applications in high frequency electronics, and memories based on ferroelectric materials. The second section deals with materials, structure ͑domains, in particular͒, and size effects. Properties of thin films that are important for applications are then addressed: polarization reversal and properties related to the reliability of ferroelectric memories, piezoelectric nonlinearity of ferroelectric films which is relevant to microsystems' applications, and permittivity and loss in ferroelectric films-important in all applications and essential in high frequency devices. In the context of properties we also discuss nanoscale probing of ferroelectrics. Finally, we comment on two important emerging topics: multiferroic materials and ferroelectric one-dimensional nanostructures.
Lead-free, potassium sodium niobate piezoelectric ceramics substituted with lithium (K0.5−x∕2,Na0.5−x∕2,Lix)NbO3 or lithium and tantalum (K0.5−x∕2,Na0.5−x∕2,Lix)(Nb1−y,Tay)O3 have been synthesized by traditional solid state sintering. The compositions chosen are among those recently reported to show high piezoelectric properties [Y. Saito, H. Takao, T. Tani, T. Nonoyama, K. Takatori, T. Homma, T. Nagaya, and M. Nakamura, Nature (London) 42, 84 (2004); Y. Guo, K. Kakimoto, and H. Ohsato, Appl. Phys. Lett. 85, 4121 (2004); Mater. Lett. 59, 241 (2005)]. We show that high densities and piezoelectric properties can be obtained for all compositions by pressureless sintering in air, without cold isostatic pressing, and without any sintering aid or special powder treatment. Resonance and converse piezoelectric (strain-field) measurements show a thickness coupling coefficient kt of 53% and converse piezoelectric coefficient d33 around 200pm∕V for the Li-substituted ceramics, and a kt of 52% and d33 over 300pm∕V for the Li- and Ta-modified samples. The unipolar strain-field hysteresis is small and comparable to that measured under similar conditions in hard Pb(Zr,Ti)O3. A peak of piezoelectric properties can be noted close to the morphotropic phase boundary. These ceramics look very promising as possible, practicable, lead-free replacements for lead zirconate titanate.
Hetero interfaces between metal-oxides display pronounced phenomena such as semiconductor-metal transitions, magnetoresistance, the quantum hall effect and superconductivity. Similar effects at compositionally homogeneous interfaces including ferroic domain walls are expected. Unlike hetero interfaces, domain walls can be created, displaced, annihilated and recreated inside a functioning device. Theory predicts the existence of 'strongly' charged domain walls that break polarization continuity, but are stable and conduct steadily through a quasi-two-dimensional electron gas. Here we show this phenomenon experimentally in charged domain walls of the prototypical ferroelectric BaTiO3. Their steady metallic-type conductivity, 109 times that of the parent matrix, evidence the presence of stable degenerate electron gas, thus adding mobility to functional interfaces.
The temperature coefficient of the dielectric permittivity (τ
ε
) of nonferroelectric complex perovskites is of importance in the application of these cermaics to microwave filters and resonators. Recent work has directly related changes in the τ
ε
of complex perovskites to the onset of structural phase transitions which involve tilting of the octahedra. It can be argued that the onset of octahedral tilting is controlled by the tolerance factor (t). Thus, a relationship between τ
ε
and t is postulated. This relationship is discussed and transmission electron microscopy is used to demonstrate examples of the structural modifications which cause the anomalies in τ
ε
at given values of t.
The reduction in switchable polarization of ferroelectric thin films due to electrical stress (polarization fatigue) is a major problem in ferroelectric nonvolatile memories. There is a large body of available experimental data and a number of existing models which address this issue, however the origin of this phenomena is still not properly understood. This work synthesizes the current experimental data, models, and approaches in order to draw conclusions on the relative importance of different macro- and microscopic scenarios of fatigue. Special attention is paid to the role of oxygen vacancy migration and electron injection into the film and it is concluded that the latter plays the predominant role. Experiments and problems for theoretical investigations, which can contribute to the further elucidation of polarization fatigue mechanisms in ferroelectric thin films, are suggested.
In Pb(Sc0.5Ta0.5)O3 it has been shown that the degree of order in the B-site Sc3+, Ta5+ cations can be controlled by suitable thermal annealing. For samples which have been well-ordered by long annealing, dielectric measurements on single crystals show a normal first-order ferroelectric phase change at 13 °C and a maximum low-temperature spontaneous polarization of 23.0 μc/cm2. With increasing disorder, the crystals begin to exhibit the classical diffuse phase transition of a ferroelectric relaxor, with a broad Curie range and strong low-frequency dielectric dispersion in the transition range. X-ray diffraction measurements of the size of the ordered microregions suggest that ordering proceeds by different mechanisms in single-crystal versus ceramic samples, though the resulting effects upon the dielectric behavior are very similar.
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