Ultra-high strain responses in lead-free (Bi0.5Na0.5)TiO3-BaTiO3-NaNbO3 ferroelectric thin films

Lead-free (Bi_0.5Na_0.5)TiO₃ (BNT)-based piezoelectric materials, have a great potential for high-precision actuators’ applications. In this work, the high-quality (0.94-x%)(Bi_0.5Na_0.5)TiO₃-0.06BaTiO₃-x%NaNbO₃ (x = 2–10, BNT-6BT-xNN) thin films have been successfully deposited on Pt/TiO₂/SiO₂/Si substrates by sol-gel method. An ultra-high poling strain S_pol value of 1.7% with a unipolar strain S_uni value of 1.47% was reported in the BNT-6BT-6NN thin films. The coexistence of the ferroelectric phase and relaxor state was observed in the compositions of x = 2–8. Furthermore, the BNT-6BT-6NN thin films show more active domain switching compared to other compositions. It is demonstrated that the optimized strain responses in the BNT-6BT-6NN are attributed to a synergistic reaction of active domain switching and reversible electric-field-induced phase transition between the ferroelectric phase and relaxor state. Our systematic study demonstrates that the BNT-6BT-xNN thin films with an improved strain response are promising candidates for the applications of miniaturized actuators.     

Electrical properties and temperature stability of SrTiO3-modified (Bi1/2Na1/2)TiO3-BaTiO3-(K1/2Na1/2)NbO3 piezoceramics

SrTiO₃-modified lead-free piezoelectric ceramics, (0.93-x)Bi_0.5Na_0.5TiO₃-xSrTiO₃-0.06BaTiO₃-0.01 K_0.5Na_0.5NbO₃ [(BNT-xST)-BT-KNN, x = 0-0.06], were prepared using a conventional solid-state reaction method. The XRD structure analysis and electric properties characteristics revealed the ST-induced phase transformation from the ferroelectric phase to the relaxor phase and their coexistence state. Benefiting from the ST-destructed ferroelectric long-range orders, the high normalized strain value of 600 pm/V was obtained in the (BNT-0.02ST)-BT-KNN ceramic at 5 kV/mm. The ST-generated relaxor phase was found to have a constructive effect on improving the temperature stability and restraining the hysteresis of the electric-field-induced strain. The normalized strain of (BNT-0.06ST)-BT-KNN ceramics could be kept at a high value ~337 pm/V at elevated temperature up to 120°C.     

Thickness-dependent switching behavior of 0.8(Bi0.5Na0.5)TiO3-0.2SrTiO3 lead-free piezoelectric thin films

0.8(Bi_0.5,Na_0.5)TiO₃-0.2SrTiO₃ (BNT-0.2ST) thin films, with thicknesses ranging from 90 to 364 nm, were fabricated on platinized silicon substrates by sol-gel method. These films were investigated by switching spectroscopy piezoresponse force microscope (SS-PFM) as a function of frequency at room temperature, revealing the enhanced ferroelectric response in ∼ 210 nm film at all frequencies (0.1 Hz - 1.5 Hz). This enhancement was ascribed to the largest thermally-activated stress at such thicknesses generated during film fabrications. As the temperature of the investigated films increases from room temperature to 200 ^oC, the piezoelectric parameters were obtained from SS-PFM, such as switching polarization (R_s), coercive bias (V₀), work of switching (A_s), maximum strain (S_max), and negative strain (S_neg), indicating an occurrence of phase transition from ferroelectrics to relaxors. This work revealed that thickness plays a crucial role for ferroelectric response and temperature-dependent phase transition in BNT-0.2ST films, since it affects the stress state and switching behavior.     

Shock-driven depolarization behaviors and electrical output in BiAlO3-doped Bi0.5Na0.5TiO3 ferroelectric ceramics

Ferroelectric materials under shock compression can generate current and power by a drastic change of the remnant polarizations and surface bound charge. This behavior has been employed in applications involving nuclear fusion trigger, energy storage devices, and high pulse power sources. Despite the large power output in lead-containing ferroelectrics, lead-free materials are highly desirable owing to the environmental concerns. Herein, the phase transition behaviors and current outputs of 0.92Bi_0.5Na_0.5TiO₃-0.08BiAlO₃ (BNT-8BA) materials are studied under high pressure. The BNT-8BA ferroelectric ceramics can be completely depolarized from polar to the nonpolar state under shock compression, resulting in a current output in the external circuit. The phase-transition-induced depolarization pressures of BNT-8BA are lower than those of the pure Bi_0.5Na_0.5TiO₃ under both dynamic and static high-pressure loads. These results can allow the understanding of the high-pressure behavior of BNT-8BA for application as ferroelectric pulsed power supply.     

Large electric-field-induced strain in B-site complex-ion (Fe0.5Nb0.5)4+-doped Bi1/2 (Na0.82K0.12)1/2TiO3 lead-free piezoceramics

In order to obtain a new system of (Bi_1/2Na_1/2)TiO₃ (BNT) based lead-free incipient piezoceramics with large strain for practical applications of actuators, we investigated the effect of B-site complex-ion (Fe_0.5Nb_0.5)⁴⁺ (FN)-doped Bi_1/2 (Na_0.82K_0.12)_1/2TiO₃ ceramics on the phase structure, dielectric, ferroelectric, piezoelectric and electric-field-induced strain properties. All samples exhibited single perovskite phase with pseudocubic symmetry. The room temperature electric-field-induced polarization (P-E) and strain (S-E) hysteresis loops indirectly illustrated ferroelectric-to-relaxor (FE-RE) phase transition. The increasing content of FN doping decreased the FE-RE phase transition temperature, T_F-R to below room temperature and induced the reversible FE-RE phase transition, giving rise to a large strain of 0.462% with a normalized strain, d^*₃₃ of 660 pm/V at a critical composition of x = 5. A fluctuation of the dielectric curve for BNKT-5 mol% FN ceramics in the spectra around 80 °C before and after polarization suggested that the large strain response can be induced via delicate mixing of the FE and RE phase.     

Phase transition and energy storage properties of Bi0.5Na0.5TiO3–Bi(Mg2/3Nb1/3)O3 lead-free ceramics

Bi_0.5Na_0.5TiO₃ (BNT) lead-free ceramics have been extensively studied due to their excellent dielectric, piezoelectric and ferroelectric properties. The phase structure and functionalities of BNT can be feasibly adjusted by doping/forming solid solutions with other elements/components. In this work, Bi(Mg_2/3Nb_1/3)O₃ (BMN) was introduced into BNT by a conventional solid-state reaction to form a homogeneous solid solution of (1-x)(Bi_0.5Na_0.5)TiO₃-xBi(Mg_2/3Nb_1/3)O₃ (BNT-xBMN) with a perovskite structure. With the increase of BMN content, a phase transition from rhombohedral R3c to tetragonal P4bm has been confirmed by XRD, along with shifting the ferroelectric-paraelectric phase transition temperature to lower temperatures with broadening dielectric peaks. Furthermore, an optimized recoverable energy density of 1.405 J/cm³ was achieved for BNT-0.10BMN ceramics under a low applied electric field of 140 kV/cm, which is mainly attributed to the transformation from ferroelectric to ergodic relaxor phase.     

Large strain and low hysteresis in (0.64-x) Bi0.5Na0.5TiO3- 0.36Sr0.7Bi0.2TiO3- x(K0.5La0.5)(Ti0.9Zr0.1)O3 piezoceramics

In this work, (0.64-x)Bi_0.5Na_0.5TiO₃- 0.36Sr_0.7Bi_0.2TiO₃- x(K_0.5La_0.5)(Ti_0.9Zr_0.1)O₃ lead-free piezoceramics were designed and fabricated by a conventional solid-phase sintering process. It is found that large strains (0.33 %), low hysteresis coefficients (32 %), and large dynamic d₃₃* (367 p.m./V) were obtained at x = 0.01. The large strain originates from the reversible transition of the relaxor to the long-range ferroelectric order in the electric field. When the ferroelectric and relaxor phases coexist in a proper ratio, they can provide a favorable condition for the easier movement of the domains and improve the strain properties. In addition, after 10⁵ cycles, the bipolar strain loop of x = 0.01 content changed slightly, demonstrating excellent fatigue resistance. This work provides a new way to design piezoelectric ceramics with large strain and low hysteresis.     

Large strain of temperature insensitive in (1–x)(0.94Bi0.5Na0.5TiO3–0.06BaTiO3) –xSr0.7La0.2TiO3 lead-free ceramics

Novel (1–x)(0.94Bi_0.5Na_0.5TiO₃–0.06BaTiO₃)–xSr_0.7La_0.2TiO₃ ternary lead-free ceramics (BNBT–xSL, x?=?0.00–0.08) were fabricated by the widely used solid-state sintering technique. The crystal phase, microstructure, dielectric relaxation, piezoelectric, and electromechanical properties of each composition were systematically analyzed. It is found that the addition of SL has little effect on the crystal phase and grain morphology, but it can remarkably improved the relaxation property of the ceramic sample and gave rise to favourable dielectric properties in a wide range of temperatures. In addition, as the SL content increases, the ferroelectric to relaxor temperature (T_F-R) is adjusted to below ambient temperature. More importantly, the decay of ferroelectric phase resulted in a significant increase in strain value: the large strain of 0.5% with normalized strain of 625?pm/V was obtained at 80kv/cm and x?=?0.04. Finally, the composition exhibited high strain of temperature insensitivity range from room temperature to 100?°C, the strain value remained above 0.4% and kept within 5%. The results are due to the coexistence of rhombohedral polar-nanoregions (PNRs) and tetragonal PNRs during the relaxor region. This result is of great importance to the developments of temperature-insensitive strain sensors and actuators.     

High energy storage properties of lead-free Mn-doped (1-x)AgNbO3-xBi0.5Na0.5TiO3 antiferroelectric ceramics

In this work, 0.2 wt.% Mn-doped (1-x)AgNbO₃-xBi_0.5Na_0.5TiO₃ (x = 0.00–0.04) ceramics were synthesized via solid state reaction method in flowing oxygen. The evolution of microstructure, phase transition and energy storage properties were investigated to evaluate the potential as high energy storage capacitors. Relaxor ferroelectric Bi_0.5Na_0.5TiO₃ was introduced to stabilize the antiferroelectric state through modulating the M₁-M₂ phase transition. Enhanced energy storage performance was achieved for the 3 mol% Bi_0.5Na_0.5TiO₃ doped AgNbO₃ ceramic with high recoverable energy density of 3.4 J/cm³ and energy efficiency of 62% under an applied field of 220 kV/cm. The improved energy storage performance can be attributed to the stabilized antiferroelectricity and decreased electrical hysteresis ΔE. In addition, the ceramics also displayed excellent thermal stability with low energy density variation (<6%) over a wide temperature range of 20−80 °C. These results indicate that Mn-doped (1-x)AgNbO₃-xBi_0.5Na_0.5TiO₃ ceramics are highly efficient lead-free antiferroelectric materials for potential application in high energy storage capacitors.     

Effects of sintering temperature and KBT content on microstructure and electrical properties of (Bi.5Na.5)TiO3-BaTiO3-(Bi.5K.5)TiO3 Pb-free ceramics

A route exploring the morphotropic phase boundaries (MPB) region in (Bi_.5Na_.5)TiO₃-BaTiO₃-(Bi_.5K_.5)TiO₃ ternary system has been designed based on the phase diagram. X-ray diffraction (XRD) has been performed to determine the phases of the prepared samples. The dielectric, ferroelectric, and piezoelectric properties of [(1-x) 0.9363(Bi_.5Na_.5)TiO₃–0.0637BaTiO₃]-x(Bi_.5K_.5)TiO₃ (BNKBT100x) ternary lead-free piezoelectric ceramics are investigated as the functions of x and sintering temperature. When x was varied from 0 to 0.11, the BNKBT100x ceramics show single perovskite structure sintered at 1130–1210?°C. These ceramics show large dielectric permittivity, small dielectric loss, and diffused phase transition behavior. Well-defined ferroelectric polarization-electric field (P-E) hysteresis loop and relative large piezoelectric and electromechanical coefficients are also found in these ceramics. When increasing x, the electrical performances first increase, then decrease. The same rule is found when varying the sintering temperature. The optimized composition and sintering temperature are finally obtained.     

NaNbO3 templates-induced phase evolution and enhancement of electromechanical properties in <00l> grain oriented lead-free BNT-based piezoelectric materials

Recently developed Bi_0.5Na_0.5TiO₃(BNT)-based piezoceramics face two urgent obstacles: high driving field required to trigger large strain and poor temperature stability. Highly oriented (1-x)(0.83Bi_0.5Na_0.5TiO₃-0.17Bi_0.5K_0.5TiO₃)-xNaNbO₃ (BNT-BKT-xNN) piezoceramics were synthesized using NN templates to resolve both obstacles. Measurements of polarization and strain hysteresis loops as well as phase transition temperature revealed a phase evolution from ergodic relaxor to ferroelectric phases, generating a high strain of 0.43% and large S_max/E_max = 720pm/V for textured BNT-BKT-4NN ceramics. The field-dependent strain was largely depended on the degree of texturing. Most intriguingly, grain-oriented specimens provided excellent actuating performance characterized by both large S_max/E_max = 693 pm/V at a low driving field of 45 kV/cm and enhanced temperature stability with S_max/E_max = 537pm/V at 120 °C. This was basically ascribed to the facilitated switching between ergodic relaxor and ferroelectric phases owing to the grain-oriented structure. As a consequence, design of <00l> oriented microstructure opens the possibility to produce efficient BNT-based piezoceramics for transferral into real-world applications.     

Electric-field-temperature phase diagram and electromechanical properties in lead-free (Na0.5Bi0.5)TiO3-based incipient piezoelectric ceramics

In this work, the (1-x)(0.8Na_0.5Bi_0.5TiO₃-0.2K_0.5Bi_0.5TiO₃)-xSrTiO₃ (NKBT-xST) incipient piezoelectric ceramics with x = 0–0.07 (0ST-7ST) were prepared by the solid-state reaction method and their structural transformation and electromechanical properties were investigated as a function of ST content. As the ST content increases, the long-range ferroelectric order is disrupted, and the ferroelectric-relaxor phase transition temperature (T_FR) shifts to around room temperature for NKBT-5ST ceramics, accompanied by a relatively high electrostrain of 0.3% at 6 kV/mm. The large strain response associated with the vanished ferroelectric properties around T_FR can be attributed to the reversible relaxor-ferroelectric phase transition. The electric-field-temperature (E-T) phase diagrams were established, and the transition between the two field-induced long-range ferroelectric states were found to take place via a two-step switching process through an intermediate relaxor state. The threshold electric field to trigger the conversion between ferroelectric state and relaxor state depends strongly on the dynamics of polarization relaxation, which is influenced by temperature and composition.     

Piezoelectric properties and microstructures of ZnO-doped Bi0.5Na0.5TiO3 ceramics

This article studies the microstructure and piezoelectric properties of a ceramic lead-free NBT under different amount of ZnO doping. X-ray diffraction shows that Zn²⁺ diffuses into the lattice of (Bi_0.5Na_0.5)TiO₃ to form a solid solution with a pure perovskite structure. By modifying the zinc oxide content, the sintering behavior of (Bi_0.5Na_0.5)TiO₃ ceramics was significantly improved and the grain size was increased. The piezoelectric coefficient d₃₃ for the 1.0 wt.% ZnO-doped (Bi_0.5Na_0.5)TiO₃ ceramics sintered at 1050 °C was found to be 95 pC/N, and the electromechanical coupling factor k_p = 0.13. However, the piezoelectric coefficient d₃₃ for the 0.5 wt.% ZnO-doped (Bi_0.5Na_0.5)TiO₃ ceramics sintered at 1140 °C was found to be 110 pC/N, and the electromechanical coupling factor k_p = 0.17.     

Large electric field-induced strain in ternary Bi0.5Na0.5TiO3-BaTiO3-Sr2MnSbO6 lead-free ceramics

The large electric-field-induced strain of Bi_0.5Na_0.5TiO₃-BaTiO₃ based ceramic make it a potential replacement for lead-based ferroelectrics in actuator applications. Herein, a ternary system (1-x)(Bi_0.5Na_0.5)_0.935Ba_0.065TiO₃-xSr₂MnSbO₆ (BNBT6.5-xSMS) ceramic was fabricated using conventional solid-state reaction. It was found that the ferroelectric to relaxor phase transition temperature T_F-R gradually shifted to lower temperature by increasing SMS contents. The ferroelectricity and piezoelectricity of BNBT6.5 were highly affected by trace amount of SMS doping. For composition BNBT6.5-0.003SMS, where T_F-R was near room temperature, a large electric-field-induced unipolar strain of ~0.4% with high normalized strain (S_max/E_max) of 728 pm/V, which is comparable to lead-based ferroelectric/antiferroelectric ceramics, was achieved owing to the reversible electric-field-induced phase transition between a non-polar relaxor phase to a polar phase with long-range ferroelectric order.     

Low hysteresis and temperature stable electrostrain in 0.97(0.94Na0.5Bi0.5TiO3-0.06BaTiO3)-0.03AgNbO3/xZnO composite ceramics

Na_0.5Bi_0.5TiO₃-based solid solutions are one of the most promising lead-free piezoelectric candidates since they can be easily tailored to exhibit large electrostrain. However, the large hysteresis and temperature-dependence of the electrostrain response are longstanding obstacles for their practical applications. In the present study, 0–3 type composites were developed with 0.97(0.94Na_0.5Bi_0.5TiO₃-0.06BaTiO₃)-0.03AgNbO₃ (NBT-6BT-3AN) matrix phase and ZnO inclusions. The optimum addition of 5 wt.% ZnO in the composites leads to reduction in hysteresis of electrostrain by 35% in comparison with pure NBT-6BT-3AN at room temperature. Meanwhile, electrostrain of the composites maintains superior temperature stability, with a variance of less than ±10% in the temperature range between 25 and 125 °C. The reason for the improvement of electrostrain is proposed to be attributed to the ergodic/nonergodic mixture phases induced by residual stress between the inclusion and matrix, as well as the phase evolution caused by the incorporation of Zn²⁺ into the matrix. Therefore, this work provides a new strategy to improve the electromechanical properties of Na_0.5Bi_0.5TiO₃-based ceramics.     

BaTiO3 nanowires-induced phase transition and thermally stable strain in (Bi0.5Na0.5)TiO3 piezoelectric ceramics

Environment-friendly lead-free piezoceramics with high strain response and extremely excellent stability in a wide operating temperature range are critically important in practical actuator applications. Here, we develop a new strategy to tune the electrostrictive strain behavior in Bi_0.5Na_0.5TiO₃ (BNT)-based ceramics via using high aspect ratio BaTiO₃ nanowires (BT NWs) as a modifier. The addition of BT NWs generates a crossover from a typical ferroelectric (BT conventional spherical particles) to a complete ergodic relaxor (ER) phase at ambient temperature, accompanied by a large electrostrictive strain of ∼0.17% with d₃₃*(S_max/E_max) = 284 pm/V. Such a high electrostrictive strain is extremely thermally stable with only <7% fluctuation from 27 °C to 120 °C. In addition, the BT NWs-modified ceramics also exhibit acceptable fatigue endurance (<30% up to 10⁵ cycles) and frequency dependence (<20% at 10Hz–100Hz). These achieved exceptional performances can be ascribed to the BT NWs-driven complete ER phase at room temperature. The findings of this study can inspire enhanced interest in nanowires as a viable modifier to BNT-based materials due to promising potential for practical actuator applications in a wide temperature range.     

Characterization of crystal structure,electrical and electromechanical properties of Mg-doped 0.94Na1/2Bi1/2TiO3-0.06BaTiO3

The use of lead-free piezoelectric materials in high-power applications requires a high mechanical quality factor Q_m and temperature-stable ferroelectric properties. In this article, the influence of Mg-doping on the 0.94Na_1/2Bi_1/2TiO₃-0.06BaTiO₃ system is analysed with focus on the role of defects related to ferroelectric hardening. Temperature stability (depolarization temperature), electromechanical properties (piezoelectric activity, Q_m), electrical properties (conductivity) and crystal structure for compositions were quantified. Compositions with similar amount of Zn-doping were analyzed for reference. A drastic increase in electrical conductivity at ?0.3/?0.5 mol% Mg was associated with a concomitant increase in Q_m. Similar behavior in Zn-doped compositions provides a basis for a more comprehensive mechanistic understanding of acceptor doping in these lead-free piezoceramics. The very high and almost vibration-velocity-independent Q_m above 800 makes Mg-doped 0.94Na_1/2Bi_1/2TiO₃-0.06BaTiO₃ an excellent candidate for high-power application.     

Large field-induced strain with enhanced temperature-stable dielectric properties of AgNbO3-modified (Bi0.5Na0.5)0.94Ba0.06TiO3 lead-free ceramics

(1-x)(Bi_0.5Na_0.5)_0.94Ba_0.06TiO₃-xAgNbO₃ lead-free piezoelectric ceramics (abbreviated as BNBT-100xAN) were prepared using the conventional solid-state sintering method. The effects of the introduction of AgNbO₃ (AN) dopants for the dielectric and piezoelectric performances of BNBT-100xAN ceramics were systematically studied. The XRD patterns and Raman spectra demonstrated that AN as a modifier was successfully diffused into the BNBT-100xAN lattice and revealed a pseudo-cubic symmetry structure. All samples exhibited a dense surface morphology accompanied by the uniform distribution of elements. A large bipolar strain of ~0.501% and unipolar strain of ~0.481% corresponding to the normalized strain d₃₃* of ~740 p.m./V were achieved for BNBT-1AN ceramic at 65 kV/cm field. The BNBT-4AN ceramic exhibited an excellent temperature-stable permittivity with the range from 59 to 380 °C and its dielectric loss was less than 0.02 between 97 °C and 329 °C. These results revealed that BNBT-100xAN ceramics were more hopeful candidates for actuators, strain sensors, and high-temperature capacitors.     

Thermally-stable large strain in Bi(Mn0.5Ti0.5)O3 modified 0.8Bi0.5Na0.5TiO3-0.2Bi0.5K0.5TiO3 ceramics

(1-x)[0.8Bi_0.5Na_0.5TiO₃-0.2Bi_0.5K_0.5TiO₃]-xBi(Mn_0.5Ti_0.5)O₃ (x = 0–0.06, BNKMT100x) lead-free ferroelectric ceramics were prepared via solid state reaction method. Bi(Mn_0.5Ti_0.5)O₃ induces a structure transition from rhombohedral-tetragonal morphotropic phases to pseudo-cubic phase. Moreover, the wide range of compositions within x = 0.03–0.055 exhibit large strain of 0.31%–0.41% and electrostrictive coefficient of 0.027–0.041 m⁴/C². Especially, at x = 0.04, the large strain and electrostrictive coefficient are nearly temperature-independent in the range of 25–100 °C. The impedance analysis shows the large strain and electrostrictive coefficient originate from polar nanoregions response due to the addition of Bi(Mn_0.5Ti_0.5)O₃.     

Giant electromechanical strain response in lead‐free SrTiO3‐doped (Bi0.5Na0.5TiO3–BaTiO3)–LiNbO3 piezoelectric ceramics

Lead‐free 0.985[(0.94?x)Bi_0.5Na_0.5TiO₃–0.06BaTiO₃–xSrTiO₃]–0.015LiNbO₃ [(BNT–BT–xST)–LN, x=0‐0.05] piezoelectric ceramics were prepared using a conventional solid‐state reaction method. It was found that the long‐range ferroelectric order in the unmodified (BNT–BT)–LN ceramic was disrupted and transformed into the ergodic relaxor phase with the ST substitution, which was well demonstrated by the dramatic decrease in remnant polarization (P_r), coercive field (E_c), negative strain (S_neg) and piezoelectric coefficient (d₃₃). However, the degradation of the ferroelectric and piezoelectric properties was accompanied by a significant increase in the usable strain response. The critical composition (BNT–BT–0.03ST)–LN exhibited a maximum unipolar strain of ~0.44% and corresponding normalized strain, S_max/E_max of ~880 pm/V under a moderate field of 50 kV/cm at room temperature. This giant strain was associated with the coexistence of the ferroelectric and ergodic relaxor phases, which should be mainly attributed to the reversible electric‐field‐induced transition between the ergodic relaxor and ferroelectric phases. Furthermore, the large field‐induced strain showed relatively good temperature stability; the S_max/E_max was as high as ~490 pm/V even at 120°C. These findings indicated that the (BNT–BT–xST)–LN system would be a suitable environmental‐friendly candidate for actuator applications.