Transmission electron microscopy study of domain structures in ferroelectric SrBi2Nb2O9 ceramics

A transmission electron microscopy study has been carried out on the domain structures of SrBi2Nb2O9 (SBN) ferroelectric ceramics which belong to the Aurivillius family of bismuth layered perovskite oxides. SBN is a potential candidate for Ferroelectric Random access memory (FeRAM) applications. The 90° ferroelectric domains and antiphase boundaries (APBs) were identified with dark field imaging techniques using different superlattice reflections which arise as a consequence of octahedral rotations and cationic shifts. The 90° domain walls are irregular in shape without any faceting. The antiphase boundaries are less dense compared to that of SrBi2Ta2O9(SBT). The electron microscopy observations are correlated with the polarization fatigue nature of the ceramic where the domain structures possibly play a key role in the fatigue- free behavior of the Aurivillius family of ferroelectric oxides.

Antiferroelectriclike polarization behavior in compositionally varying (1-x) Pb(Mg1/3Nb2/3)O3–(x) PbTiO3 multilayers

Compositionally varying multilayers of (1−x) Pb(Mg1/3N2/3)O3–(x) PbTiO3 were fabricated using pulsed laser ablation technique. An antiferroelectriclike polarization hysteresis was observed in these relaxor based multilayer systems. The competition among the intrinsic ferroelectric coupling in the relaxor ferroelectrics and the antiferroelectric coupling among the dipoles at the interface gives rise to an antiferroelectriclike polarization behavior. An increment in the coercive field and the applied field corresponding to the polarization flipping at low temperatures, provide further insight on the competition among the long-range ferroelectric interaction and the interfacial interaction in the polarization behavior of these relaxor multilayers.

Growth and ferroelectric properties of Bi2VO5.5 thin films with metallic LaNiO3 electrodes

Novel ferroelectric bismuth vanadate, Bi2VO5.5 (BVO), thin films have been grown between lattice matched metallic LaNiO3 (LNO) layers deposited on SrTiO3 (STO) by the pulsed laser deposition technique. LNO/BVO/LNO/STO and Au/BVO/LNO/STO trilayer structures exhibited c‐oriented (001) growth of BVO. LNO has been found to be a good metallic electrode with sheet resistance ∼20 Ω in addition to aiding c‐axis oriented BVO growth. The dielectric constant, ϵr of LNO/BVO/LNO/STO, at 300 K was about 12. However, when an Au electrode was used on top of BVO/LNO/STO film, it showed a significant improvement in the dielectric constant (ϵr=123). The ferroelectric properties of BVO thin films have been confirmed by hysteresis behavior with a remnant polarization, Pr=4.6×10−8 C/cm2 and coercive field, Ec=23 kV/cm at 300 K.

Improved ferroelectric and leakage properties in symmetric BiFeO3/SrTiO3 superlattice

Symmetric BiFeO3/SrTiO3 superlattices were fabricated by pulsed laser deposition on SrTiO3 (100) substrates. Frequency independent and near saturated P-E hysteresis was observed in the case of a superlattice (periodicity of ∼ 11 nm) as compared to leaky hysteresis observed in epitaxial BiFeO3. Room temperature leakage current density of the superlattice was almost two orders of magnitude lower than that of BiFeO3. Observed leakage current behavior in case of both BiFeO3 and superlattice indicates the dominance of space charge limited conduction. Improvement in ferroelectric property was discussed in connection to enhanced epitaxial strain, reduced leakage current, and electrostatic interaction between BiFeO3 and SrTiO3.

Ferroelectric interaction and polarization studies in BaTiO3/SrTiO3 superlattice

Ferroelectric superlattice structures consisting of alternating layers of BaTiO3 and SrTiO3 with variable interlayer thickness were grown on Pt (111)/TiO2/SiO2/Si (100) substrates by pulsed laser deposition. The presence of superlattice reflections in the x-ray diffraction pattern clearly showed the superlattice behavior of the fabricated structures over a range of 6.4–20 nm individual layer thicknesses. Depth profile conducted by secondary ion mass spectrometry analysis showed a periodic concentration of Ba and Sr throughout the film. Polarization hysteresis and the capacitance-voltage characteristics of these films show clear size dependent ferroelectric characteristics. The spontaneous (Ps) and remnant (Pr) polarizations increase gradually with decreasing periodicity, reach a maximum at a finite thickness and then decrease. The competition between the size effect and long-range ferroelectric interaction is suggested as a possible reason for this phenomenon. The temperature dependence of Ps and Pr shows a single ferroelectric phase transition, and the Curie temperature is estimated to be about 316 K. The curve shows that the ferroelectric superlattice tends to form an artificial material, responding as a single structure with an averaged behavior of both the parent systems.

Metastable monoclinic and orthorhombic phases and electric field induced irreversible phase transformation at room temperature in the lead-free classical ferroelectric BaTiO3

For decades it has been a well-known fact that among the few ferroelectric compounds in the perovskite family, namely, BaTiO3, KNbO3, PbTiO3, and Na1/2Bi1/2TiO3, the dielectric and piezoelectric properties of BaTiO3 are considerably higher than the others in polycrystalline form at room temperature. Further, similar to ferroelectric alloys exhibiting morphotropic phase boundary, single crystals of BaTiO3 exhibit anomalously large piezoelectric response when poled away from the direction of spontaneous polarization at room temperature. These anomalous features in BaTiO3 remained unexplained so far from the structural standpoint. In this work, we have used high-resolution synchrotron x-ray powder diffraction, atomic resolution aberration-corrected transmission electron microscopy, in conjunction with a powder poling technique, to reveal that at 300 K (i) the equilibrium state of BaTiO3 is characterized by coexistence of metastable monoclinic Pm and orthorhombic (Amm2) phases along with the tetragonal phase, and (ii) strong electric field switches the polarization direction from the 001] direction towards the 101] direction. These results suggest that BaTiO3 at room temperature is within an instability regime, and that this instability is the fundamental factor responsible for the anomalous dielectric and piezoelectric properties of BaTiO3 as compared to the other homologous ferroelectric perovskite compounds at room temperature. Pure BaTiO3 at room temperature is therefore more akin to lead-based ferroelectric alloys close to the morphotropic phase boundary where polarization rotation and field induced ferroelectric-ferroelectric phase transformations play a fundamental role in influencing the dielectric and piezoelectric behavior.

Tuning of dielectric, pyroelectric and ferroelectric properties of 0.715Bi(0.5)Na(0.5)TiO(3)-0.065BaTiO(3)-0.22SrTiO(3) ceramic by internal clamping

This study systematically investigates the phenomenon of internal clamping in ferroelectric materials through the formation of glass-ceramic composites. Lead-free 0.715Bi(0.5)Na(0.5)TiO(3)-0.065BaTiO(3)-0.22SrTiO(3) (BNT-BT-ST) bulk ferroelectric ceramic was selected for the course of investigation. 3BaO - 3TiO(2) - B2O3 (BTBO) glass was then incorporated systematically to create sintered samples containing 0%, 2%, 4% and 6% glass (by weight). Upon glass induction features like remnant polarization, saturation polarization, hysteresis losses and coercive field could be varied as a function of glass content. Such effects were observed to benefit derived applications like enhanced energy storage density similar to 174 k J/m(3) to similar to 203 k J/m(3) and pyroelectric coefficient 5.7x10(-4) Cm-2K-1 to 6.8x10(-4) Cm-2K-1 by incorporation of 4% glass. Additionally, BNT-BT-ST depolarization temperature decreased from 457K to 431K by addition of 4% glass content. Glass incorporation could systematically increases diffuse phase transition and relaxor behavior temperature range from 70 K to 81K and 20K to 34 K, respectively when 6% and 4% glass content is added which indicates addition of glass provides better temperature stability. The most promising feature was observed to be that of dielectric response tuning. It can be also used to control (to an extent) the dielectric behavior of the host ceramic. Dielectric permittivity and losses decreased from 1278 to 705 and 0.109 to 0.107 for 6% glass, at room temperature. However this reduction in dielectric constant and loss increases pyroelectric figures of merit (FOMs) for high voltage responsivity (F-v) high detectivity (F-d) and energy harvesting (F-e) from 0.018 to 0.037 m(2)C(-1), 5.89 to 8.85 mu Pa-1/2 and 28.71 to 61.55 Jm(-3)K(-2), respectively for 4% added ceramic-glass at room temperature. Such findings can have huge implications in the field of tailoring ferroelectric response for application specific requirements. (C) 2015 Author(s).

Electromechanical influence of crack velocity at bifurcation for poled ferroelectric materials

The piezoelastodynamic field equations are solved to determine the crack velocity at bifurcation for poled ferroelectric materials where the applied electrical field and mechanical stress can be varied. The underlying physical mechanism, however, may not correspond to that assumed in the analytical model. Bifurcation has been related to the occurrence of a pair of maximum circumferential stress oriented symmetrically about the moving crack path. The velocity at which this behavior prevails has been referred to as the limiting crack speed. Unlike the classical approach, bifurcation will be identified with finite distances ahead of a moving crack. Nucleation of microcracks can thus be modelled in a single formulation. This can be accomplished by using the energy density function where fracture initiation is identified with dominance of dilatation in relation to distortion. Poled ferroelectric materials are selected for this study because the microstructure effects for this class of materials can be readily reflected by the elastic, piezoelectic and dielectric permittivity constants at the macroscopic scale. Existing test data could also shed light on the trend of the analytical predictions. Numerical results are thus computed for PZT-4 and compared with those for PZT-6B in an effort to show whether the branching behavior would be affected by the difference in the material microstructures. A range of crack bifurcation speed upsilon(b) is found for different r/a and E/sigma ratios. Here, r and a stand for the radial distance and half crack length, respectively, while E and a for the electric field and mechanical stress. For PZT-6B with upsilon(b) in the range 100-1700 m/s, the bifurcation angles varied from +/-6degrees to +/-39degrees. This corresponds to E/sigma of -0.072 to 0.024 V m/N. At the same distance r/a = 0.1, PZT-4 gives upsilon(b) values of 1100-2100 m/s; bifurcation angles of +/-15degrees to +/-49degrees; and E/sigma of -0.056 to 0.059 V m/N. In general, the bifurcation angles +/-theta(0) are found to decrease with decreasing crack velocity as the distance r/a is increased. Relatively speaking, the speed upsilon(b) and angles +/-theta(0) for PZT-4 are much greater than those for PZT-6B. This may be attributed to the high electromechanical coupling effect of PZT-4. Using upsilon(b)(0) as a base reference, an equality relation upsilon(b)(-) < upsilon(b)(0) < upsilon(b)(+) can be established. The superscripts -, 0 and + refer, respectively, to negative, zero and positive electric field. This is reminiscent of the enhancement and retardation of crack growth behavior due to change in poling direction. Bifurcation characteristics are found to be somewhat erratic when r/a approaches the range 10(-2)-10(-1) where the kinetic energy densities would fluctuate and then rise as the distance from the moving crack is increased. This is an artifact introduced by the far away condition of non-vanishing particle velocity. A finite kinetic energy density prevails at infinity unless it is made to vanish in the boundary value problem. Future works are recommended to further clarify the physical mechanism(s) associated with bifurcation by means of analysis and experiment. Damage at the microscopic level needs to be addressed since it has been known to affect the macrocrack speeds and bifurcation characteristics. (C) 2002 Published by Elsevier Science Ltd.

Energy principle of ferroelectric ceramics and single domain mechanical model

Many physical experiments have shown that the domain switching in a ferroelectric material is a complicated evolution process of the domain wall with the variation of stress and electric field. According to this mechanism, the volume fraction of the domain switching is introduced in the constitutive law of ferroelectric ceramic and used to study the nonlinear constitutive behavior of ferroelectric body in this paper. The principle of stationary total energy is put forward in which the basic unknown quantities are the displacement u (i) , electric displacement D (i) and volume fraction rho (I) of the domain switching for the variant I. Mechanical field equation and a new domain switching criterion are obtained from the principle of stationary total energy. The domain switching criterion proposed in this paper is an expansion and development of the energy criterion. On the basis of the domain switching criterion, a set of linear algebraic equations for the volume fraction rho (I) of domain switching is obtained, in which the coefficients of the linear algebraic equations only contain the unknown strain and electric fields. Then a single domain mechanical model is proposed in this paper. The poled ferroelectric specimen is considered as a transversely isotropic single domain. By using the partial experimental results, the hardening relation between the driving force of domain switching and the volume fraction of domain switching can be calibrated. Then the electromechanical response can be calculated on the basis of the calibrated hardening relation. The results involve the electric butterfly shaped curves of axial strain versus axial electric field, the hysteresis loops of electric displacement versus electric filed and the evolution process of the domain switching in the ferroelectric specimens under uniaxial coupled stress and electric field loading. The present theoretic prediction agrees reasonably with the experimental results given by Lynch.

New chiral E- and Z-isomers of the 1R,4R-2-arylidene-p-menthane-3-ones in induced cholesteric and ferroelectric liquid crystals

A novel pair of the E- and Z-isomeric 1R,4R-2-(4-heptyloxyphenyl)-benzylidene-p-menthan-3-ones has been prepared and the influence of distinctions in their molecular geometry on macroscopic properties of liquid crystal systems with the induced supra-molecular helical structure has been studied. The significantly lower helical twisting power of the chiral Z-isomer in comparison with that of E- one has been confirmed in the case of induced cholesteric systems based on 4-pentyl-4-cyanobiphenyl. The phase behavior and ferroelectric characteristics have been investigated for smectic-C* compositions based on the eutectic mixture of the homological 4-hexyloxyphenyl-4'-hexyloxy- and 4-hexyloxyphenyl-4'-octyloxybenzoates containing the novel isomeric chiral dopants. The spontaneous polarisation of the opposite signs induced by the isomeric chiral components has been revealed for the compositions studied. Distinctions in phase states, absolute values of the spontaneous polarization, smectic tilt angle and rotation viscosity of the systems obtained are discussed.

Programmable ZnO nanowire transistors using switchable polarization of ferroelectric liquid crystal

We demonstrate modulations of electrical conductance and hysteresis behavior in ZnO nanowire transistors via electrically polarized switching of ferroelectric liquid crystal (FLC). After coating a nanowire channel in the transistors with FLCs, we observed large increases in channel conductance and hysteresis width, and a strong dependence of hysteresis loops on the polarization states associated with the orientation of electric dipole moments along the direction of the gate electric field. Furthermore, the reversible switching and retention characteristics provide the feasibility of creating a hybrid system with switch and memory functions. © 2013 American Institute of Physics.

High-frequency programmable acoustic wave device realized through ferroelectric domain engineering

Surface acoustic wave devices are extensively used in contemporary wireless communication devices. We used atomic force microscopy to form periodic macroscopic ferroelectric domains in sol-gel deposited lead zirconate titanate, where each ferroelectric domain is composed of many crystallites, each of which contains many microscopic ferroelastic domains. We examined the electro-acoustic characteristics of the apparatus and found a resonator behavior similar to that of an equivalent surface or bulk acoustic wave device. We show that the operational frequency of the device can be tailored by altering the periodicity of the engineered domains and demonstrate high-frequency filter behavior (>8GHz), allowing low-cost programmable high-frequency resonators. © 2014 AIP Publishing LLC.

Abnormal ferroelectric response and enhancement of piezoelectricity of PbTiO3 under uniaxial compression

The ferroelectricity of rhombohedral PbTiO3 under uniaxial compression is investigated from first-principles study. Upon compression, the ferroelectricity decreases until a critical stress of -29 GPa and then increases with a further increase of the magnitude of the uniaxial compressive stress. We also find that uniaxial compression could enhance piezoelectricity and that the maximum piezoelectric coefficient d(33) occurs at sigma(33)=-49 GPa, which supports the experimentally observed piezoelectric behavior in rhombohedral Pb(Mg1/3Nb2/3O3)-0.32PbTiO(3) [Q. Wan, C. Chen, and Y. P. Shen, J. Appl. Phys. 98, 024103 (2005)]. Our calculated results show that the Pb, Ti, and O atoms have different contributions to the total polarization with increasing the magnitude of uniaxial compressive stress, and that when -sigma(33)>55 GPa, the Ti atoms no longer have contributions to the polarization, which leads to the changes of ferroelectricity and piezoelectricity. (C) 2008 American Institute of Physics.

Bilayer formation of two chiral ferroelectric liquid crystal molecules at the air-water interface

The bilayer formation behavior of two chiral ferroelectric liquid crystal molecules at the air-water interface was studied.

Toward Self-Assembled Ferroelectric Random Access Memories: Hard-Wired Switching Capacitor Arrays with Almost Tb/in.2 Densities

We report on the successful fabrication of arrays of switchable nanocapacitors made by harnessing the self-assembly of materials. The structures are composed of arrays of 20-40 nm diameter Pt nanowires, spaced 50-100 nm apart, electrodeposited through nanoporous alumina onto a thin film lower electrode on a silicon wafer. A thin film ferroelectric (both barium titanate (BTO) and lead zirconium titanate (PZT)) has been deposited on top of the nanowire array, followed by the deposition of thin film upper electrodes. The PZT nanocapacitors exhibit hysteresis loops with substantial remnant polarizations, while although the switching performance was inferior, the low-field characteristics of the BTO nanocapacitors show dielectric behavior comparable to conventional thin film heterostructures. While registration is not sufficient for commercial RAM production, this is nevertheless an embryonic form of the highest density hard-wired FRAM capacitor array reported to date and compares favorably with atomic force microscopy read-write densities.