Intrinsic stress-induced adaptive ferroelectric domain rearrangement in the monoclinic Pb(Mg1/3Nb2/3)O3-PbTiO3 single crystal

Response of sub-microdomains in an adaptive ferroelectric Pb(Mg_1/3Nb_2/3)O₃-34%PbTiO₃ single crystal to the temperature-induced stress field was investigated by scanning electron acoustic microscopy and piezoresponse force microscopy. Formation of different types of domain configurations (wave-like, “W”-like and lattice-like) closely related to nanodomain cooperative response after the sample subjected to frozen treatment was presented. In the adaptive ferroelectric state lattice-like domain structures demonstrated more stable behavior compared to other types of domains (wave-like and “W”-like) due to their minimum domain wall energy density, and provided a type of effective structure to remove domain topological change under the stress field.     

Improvement of the remnant polarization of 0.65Pb(Mg1/3Nb2/3)O3-0.35PbTiO3 thin films in a multilayer composite

It has been previously reported that the remnant polarization of 0.65Pb(Mg_1/3Nb_2/3)O₃-0.35PbTiO₃ (PMNT) thin films on Si-based substrates is much lower than that of bulk ceramics with the same composition, which is a problem for its integration in microdevices. The preparation of multilayer composites of PMNT and PbTiO₃ layers, which maintain large remnant polarization values even for the thinnest films, is explored in this work as an alternative for obtaining PMNT-based films with enhanced remanence. The multilayer composite thin films were fabricated onto Pt/TiO₂/SiO₂/Si (100) substrates by Chemical Solution Deposition. The deposited layers are ultrathin and the results show that there is no significant interdiffusion among them. Although the typical constraints related to the small grain size found in ultrathin layers and the associated lack of ferroelastic domains are present, the results show an improvement of the remanence of the PMNT layer in the multilayer composite film and that these composites can be good candidates for the integration of PMNT in devices.     

Domain structure of [(Na0.7K0.2Li0.1)0.5Bi0.5]TiO3 ceramics studied by piezoresponse force microscopy

The domain structure of lead-free ceramics [(Na_0.7K_0.2Li_0.1)_0.5Bi_0.5]TiO₃ was studied by piezoresponse force microscopy (PFM) method. The complicated curved domain structure was observed in the ceramics, and there are some nano domains in the sub-microsized domains, which indicate the relaxor nature of the material. The mechanism for the strong relaxation of the material was discussed in the letter. The reversal behavior of the domain was also studied by PFM method. Only part of the domains reversed after the poling process, and domains of the ceramics reversed back from the center of the domains at first.     

Morphotropic phase boundary in Pb(Sc1/2Nb1/2)O3-BiScO3-PbTiO3 high temperature piezoelectrics

The solid solutions in the 0.36BiScO₃-0.64(1 − x)PbTiO₃-0.64xPb(Sc_1/2Nb_1/2)O₃ system were fabricated using wolframite precursor method. A coexistence of rhombohedral and tetragonal phases is formed in the studied compositions range and a wide morphotropic phase boundary region is confirmed by X-ray diffraction results. After the addition of Pb(Sc_1/2Nb_1/2)O₃, a relaxor behavior is induced and the dielectric maximum temperature shifts to higher temperatures with increasing measuring frequencies. The presence of relaxor can be ascribed to the formation of polar nanoregions. The studied composition exhibits the optimal ferroelectric and piezoelectric properties with d₃₃ of 453 pC/N and K_p of 0.58, T_m of 405 °C for x = 0.10 composition, which is suitable for future high-temperature piezoelectric application.     

Large electrocaloric effect of highly (100)-oriented 0.68PbMg1/3Nb2/3O3-0.32PbTiO3 thin films with a Pb(Zr0.3Ti0.7)O3/PbOx buffer layer

0.68PbMg_1/3Nb_2/3O₃-0.32PbTiO₃ (PMN-PT) thin films with a lead zirconate titanate Pb(Zr_0.3Ti_0.7)O₃ (PZT)/PbO_x buffer layer were deposited on Pt/TiO₂/SiO₂/Si substrates by radio frequency magnetron sputtering technique, and pure perovskite crystalline phase with highly (100)-preferred orientation was formed in the ferroelectric films. We found that the highly (100)-oriented thin films possess not only excellent dielectric and ferroelectric properties but also a large electrocaloric effect (13.4 K at 15 V, i.e., 0.89 K/V) which is attributed to the large electric field-induced polarization and entropy change during the ferroelectric-paraelectric phase transition. The experimental results indicate that the use of PZT/PbO_x buffer layer can induce the crystal orientation and phase purity of the PMN-PT thin films, and consequently enhance their electrical properties.     

Ag and O ion irradiation induced improvement in dielectric properties of the Ba(Co1/3Nb2/3)O3 thin films

We present the preliminary results of temperature and frequency dependent dielectric measurements on Ba(Co_1/3Nb_2/3)O₃ (BCN) thin films. These films were prepared on indium tin oxide (ITO) coated glass substrates by the pulse laser deposition (PLD) technique. It exhibits single-phase hexagonal symmetry. These films were irradiated with Ag¹⁵⁺ (200 MeV) and O⁷⁺ (100 MeV) beams at the fluence 1 × 10¹¹, 1 × 10¹², and 1 × 10¹³ ions/cm². On irradiating these films, its dielectric constant (?′) and dielectric loss (tan δ) parameters improve compared to un-irradiated film. Compared to O⁷⁺ irradiation induced point/cluster defects Ag¹⁵⁺ induced columnar defects are more effective in reducing/pinning trapped charges within grains. The present paper highlights the role of swift heavy ion irradiation in engineering the dielectric properties of conductive samples to enable them to be useful for microwave device applications.     

Synthesis and characterization of 0.65Pb(Mg1/3Nb2/3)O3-0.35PbTiO3 fibers with Pt core

This paper reports the synthesis and electromechanical characterization of 0.65Pb(Mg_1/3Nb_2/3)O₃-0.35PbTiO₃ (PMN-35PT) ceramics and fibers. To prevent the lead loss during the sintering of the fibers, lead-atmosphere was used during the sintering process. As a consequence, it was possible to ensure a good densification of the fiber and a pure perovskite phase. The electromechanical coupling factor and piezoelectric coefficient of the piezoelectric fiber were found to be k₃₁ = 0.20 and d₃₁ = −130 pC/N, respectively. These results are lower than ceramic sample properties (k₃₁ = 0.32 and d₃₁ = −234 pC/N). In order to determine reasons for these lower results in fiber shape sample, density and poling studies were performed. It is shown that fiber shape samples cannot be poled correctly because of the ratio between core and ceramic diameters.     

Structure and electrical properties of (100)-oriented Pb(Zn1/3Nb2/3)O3–Pb(Mg1/3Nb2/3)O3–PbTiO3 thin films on La0.7Sr0.3MnO3 electrode by chemical solution deposition

(100)-oriented 0.462Pb(Zn_1/3Nb_2/3)O₃–0.308Pb(Mg_1/3Nb_2/3)O₃–0.23PbTiO₃ (PZN-PMN-PT) perovskite ferroelectric thin films were prepared on La_0.7Sr_0.3MnO₃/LaAlO₃ (LSMO/LAO) substrate via a chemical solution deposition route. The perovskite LSMO electrode was found to effectively suppress the pyrochlore phase while promote the growth of the perovskite phase in the PZN-PMN-PT film. The film annealed at 700 °C exhibited a high dielectric constant of 2130 at 1 kHz, a remnant polarization, 2P_r, of 29.8 μC/cm², and a low leakage current density of 7.2 × 10^− 7 A/cm² at an applied field of 200 kV/cm. The ferroelectric polarization was fatigue-free at least up to 10¹⁰ cycles. Piezoelectric coefficient, d₃₃, of 48 pm/V was also demonstrated. The results showed that much superior properties could be achieved with the PZN-PMN-PT thin films on the solution derived LSMO electrode than on Pt electrode by sputtering.     

Piezoelectric shear-mode properties of Pb(Yb1/2Nb1/2)O3-PbTiO3 ceramics

A Pb(Yb_1/2Nb_1/2)O₃-PbTiO₃ [PYNT] solid solution was synthesized and characterized for its potential use. The shear-mode dielectric and piezoelectric behaviors of PYNT with a morphotropic phase boundary (MPB) composition were studied as a function of temperature. Dielectric permittivity K₁₁^T and loss were found to be 2310 and 2.5%, respectively, at room temperature. Piezoelectric coefficient d₁₅ and electromechanical coupling factor k₁₅ were calculated to be 710 pC/N and 0.70, respectively, maintaining nearly constant up to 300 °C, resistivity and RC time constant were observed to be 2.4 × 10⁹ Ω cm and 1.07 s, respectively, at 350 °C. These good piezoelectric properties, together with the high Curie temperature (T_c ∼ 370 °C), indicate that PYNT is a promising candidate for high temperature-shear sensor and inkjet actuator applications.     

The influence of defects on ferroelectric and pyroelectric properties of Pb(Mg1/3Nb2/3)O3-0.28PbTiO3 single crystals

Relaxor-based ferroelectric single crystals 0.72Pb(Mg_1/3Nb_2/3)O₃-0.28PbTiO₃ (PMN-0.28PT) were grown by a modified Bridgman technique. The direct current (dc) conductivity was investigated and corresponding conduction mechanisms were discussed. V^″Pb−VO defects are dominant from 245 °C to 650 °C. The ferroelectric properties of [1 1 1]-oriented PMN-0.28PT were systematically investigated, with the coercive field (E_c) of 5.2 kV cm⁻¹ and remnant polarization (P_r) of 37.8 μC cm⁻² at room temperature. Moreover, the dielectric and pyroelectric performances of PMN-0.28PT were measured and the integrated pyroelectric performances greatly enhanced after annealing in oxygen at 500 °C for 20 h. This is due to the decrease of oxygen vacancies in the single crystals when being annealed in the oxygen-rich atmosphere. These make [1 1 1]-oriented PMN-0.28PT crystals a promising candidate for infrared detectors and thermal imagers used at room temperature.     

Triple-like hysteresis loop and microdomain-macrodomain transformation in the relaxor-based 0.76Pb(Mg1/3Nb2/3)O3-0.24PbTiO3 single crystal

Polarization and depolarization behavior of the relaxor-based 0.76Pb(Mg_1/3Nb_2/3)O₃-0.24PbTiO₃ single crystal has been studied between 25 and 200 °C by means of dielectric measurement with or without dc bias, Polarization-Electric field (P-E) hysteresis loop and discharging current measurements. Triple-like P-E loops were obtained in a temperature range between 80 and 90 °C, disclosing the transformation between microdomain state and metastable macrodomain state. For the poled crystals, the microdomain state with dipoles partially oriented was indicated to exist in the similar temperature range and mediate between the lower temperature macrodomain state with dipoles oriented and the higher temperature microdomain state with dipoles in a random system.     

Role of La0.5Sr0.5CoO3 template layers on dielectric and electrical properties of pulsed-laser ablated Pb(Nb2/3Mg1/3)O3-PbTiO3 thin films

Relaxor ferroelectric thin films of 0.7Pb(Mg_1/3Nb_2/3)O₃-0.3PbTiO₃ (PMN-PT) deposited on platinized silicon substrates with and without template layers were studied. Perovskite phase (80% by volume) was obtained through proper selection of the processing conditions on bare Pt/Ti/SiO₂/Si substrates. The films were initially grown at 300 °C using pulsed-laser ablation and subsequently annealed in a rapid thermal annealing furnace in the temperature range of 750-850 °C to induce crystallization. Comparison of microstructure of the films annealed at different temperatures showed change in perovskite phase formation and grain size etc. Results from compositional analysis of the films revealed that the films initially possessed high content of lead percentage, which subsequently decreased after annealing at temperature 750-850 °C. Films with highest perovskite content were found to form at 820-840 °C on Pt substrates where the Pb content was near stoichiometric. Further improvement in the formation of perovskite PMN-PT phase was obtained by using buffer layers of La_0.5Sr_0.5CoO₃ (LSCO) on the Pt substrate. This resulted 100% perovskite phase formation in the films deposited at 650 °C. Dielectric studies on the PMN-PT films with LSCO template layers showed high values of relative dielectric constant (3800) with a loss factor (tan δ) of 0.035 at a frequency of 1 kHz at room temperature.     

Effect of MnO2 addition on the piezoelectric properties in Pb(Mg1/3Nb2/3)O3 relaxor ferroelectrics

The effects of MnO₂ addition on the piezoelectric properties in Pb(Mg_1/3Nb_2/3)O₃ relaxor ferroelectrics were studied in the ferroelectricity-dominated temperature range from −40 to 30°C. Dielectric, piezoelectric, and electrostrictive properties were examined to clarify the effect of MnO₂ addition. As an added amount of MnO₂ increases, the dielectric constant decreases and the mechanical quality factor increases in Pb(Mg_1/3Nb_2/3)O₃. From the experimental results, it has been found that Mn behaves as a ferroelectric domain pinning element.     

Polar nanodomains and relaxor behaviour in (1 − x)Pb(Mg1/3Nb2/3)O3–xPbTiO3 crystals with x = 0.3–0.5

Phase transitions and dielectric properties of the (1 − x)Pb(Mg_1/3Nb_2/3)O₃–xPbTiO₃ crystals with x = 0.3–0.5 are studied. The solid solutions in this composition range are shown to be relaxor ferroelectrics. The crystals with low x demonstrate a diffused maximum in the temperature dependences of the dielectric permittivity at T_m. T_m varies with frequency according to the Vogel–Fulcher law. The polarizing microscopy investigations reveal a first-order phase transition from the relaxor phase to the low-temperature ferroelectric phase at T_C, which is several degrees below T_m. The permittivity peak in the crystals with x = 0.5 is sharp, and T_m is equal to T_C and does not depend on frequency, as is typical of the transition from a ferroelectric to an ordinary paraelectric phase. Nevertheless, the relaxor, but not the paraelectric, phase is observed at T > T_m. This conclusion is confirmed by the observation of the temperature behaviour of complex dielectric permittivity at T > T_m, which is typical of relaxors and related to the existence of polar nanodomains.     

Effects of Fe2O3 doping on the microstructure and piezoelectric properties of 0.55Pb(Ni1/3Nb2/3)O3-0.45Pb(Zr0.3Ti0.7)O3 ceramics

0.55Pb(Ni_1/3Nb_2/3)O₃-0.45Pb(Zr_0.3Ti_0.7)O₃(PNN-PZT) ceramics with different concentration of xFe₂O₃ doping (where x = 0.0, 0.8, 1.2, 1.6 mol%) were synthesized by the conventional solid state sintering technique. X-ray diffraction analysis reveals that all specimens are a pure perovskite phase without pyrochlore phase. The density and grain size of Fe-doped ceramics tend to increase slightly with increasing concentration of Fe₂O₃. Comparing with the undoped ceramics, the piezoelectric, ferroelectric and dielectric properties of the Fe-doped PNN-PZT specimens are significantly improved. Properties of the piezoelectric constant as high as d₃₃ ~ 956 pC/N, the electromechanical coupling factor k_p ~ 0.74, and the dielectric constant ε_r ~ 6095 are achieved for the specimen with 1.2 mol% Fe₂O₃ doping sintered at 1200 °C for 2 h.     

Growth and electrical performance of Pb(Mg1/3Nb2/3)O3-PbTiO3-Pb(Fe1/2Nb1/2)O3 single crystals

For the first time, we have grown ferroelectric single crystals Pb(Mg_1/3Nb_2/3)O₃-PbTiO₃-Pb(Fe_1/2Nb_1/2)O₃ (PMN-PT-PFN) from the melt by the simple slow cooling process. The chemical composition of the single crystals PMN-PT-PFN (0.59/0.31/0.10) is near the morphotropic phase boundary (MPB). X-ray diffraction (XRD) was used to study phase structure of the as-grown crystals, energy dispersive X-ray spectrometer (EDS) and electron probe micro-analyzer (EPMA) were employed to confirm the chemical composition and element distribution of the as-grown crystals, respectively. The ferroelectric, dielectric and piezoelectric properties of the as-grown PMN-PT-PFN (0.59/0.31/0.10) single crystal oriented along the (0 0 1) axis were measured, which showed that the remnant polarization (P_r), coercive electric fields (E_c), the Curie temperature (T_c) and the piezoelectric coefficient (d₃₃) were 50.2 μC/cm², 13.9 kV/cm, 158 °C and about 1800 pC/N, respectively. All the results indicated that the PMN-PT-PFN (0.59/0.31/0.10) single crystals are promising for applying to field of high frequency.     

Stoichiometric Pb(Mg1/3Nb2/3)O3 perovskite ceramics produced by reaction-sintering process

Stoichiometric lead magnesium niobate, Pb(Mg_1/3Nb_2/3)O₃ (PMN), perovskite ceramics produced by reaction-sintering process were investigated. Without calcination, a mixture of PbO, Nb₂O₅, and Mg(NO₃)₂ was pressed and sintered directly. Stoichiometric PMN ceramics of 100% perovskite phase were obtained for 1, 2, and 4 h sintering at 1250 and 1270 °C. PMN ceramics with density 8.09 g/cm³ (99.5% of theoretical density 8.13 g/cm³) and K_max 19,900 under 1 kHz were obtained.     

Morphotropic phase boundary and piezoelectric properties of (Bi1/2Na1/2)1 − x(Bi1/2K1/2)xTiO3-0.03(Na0.5K0.5)NbO3 ferroelectric ceramics

Lead-free piezoelectric ceramics, (Bi_1/2Na_1/2)_1 − x(Bi_1/2K_1/2)_xTiO₃-0.03(Na_0.5K_0.5)NbO₃ (x = 0.10-0.40) were synthesized by conventional solid-state sintering. A morphotropic phase boundary (MPB) between rhombohedral and tetragonal phases was confirmed. Two dielectric anomalies can be observed, showing diffused phase transition behavior. There is no shift of the dielectric maximum temperature with frequency due to the contribution of space charge at high temperatures, similar to pure (Bi_1/2Na_1/2)TiO₃. The materials near MPB show a strong compositional dependence with the optimal properties of a d₃₃ of 167 pC/N, a k_p of 35.5%, a P_r of 27.6 μC/cm² and a E_c of 27.9 kV/cm, suitable for future application.