Phase transition and piezoelectricity of BaZrO3-modified (K,Na)NbO3 lead-free piezoelectric thin films

(K,Na)NbO₃ (KNN) is a promising lead-free ferroelectric/piezoelectric system, to which incorporating BaZrO₃ can greatly enhance its piezoelectricity, but the mechanism is not clear. This work was conducted to investigate the phase transition in the BaZrO₃-modifed KNN system and its contribution to piezoelectricity enhancement, using thin films with a fixed orientation and high compositional homogeneity fabricated by a sol-gel method. Two ferroelectric-to-ferroelectric phase transitions are revealed, which correspond to monoclinic M_C- M_A phase transition at higher temperature and rhombohedral-monoclinic M_C phase transition at lower temperature. It is difficult to distinguish these phases in KNN-based bulk materials, but their differences are clear when conducting high-resolution X-ray reciprocal space mapping (RSM) on the present thin films. Piezoresponse force microscopy experiments also revealed an interesting finding that local piezoelectricity of monoclinic phases was higher than that of rhombohedral ones in KNN-based thin films. This work could shed insights on the fundamental understandings for the effect of the chemical doping, and offer guidance for property optimization in the KNN-based lead-free piezoelectrics.     

Effect of Pyrolysis Temperature on Sol–Gel Synthesis of Lead‐free Piezoelectric (K,Na)NbO3 Films on Nb:SrTiO3 Substrates

Lead‐free (K,Na)NbO₃ (KNN) piezoelectric films were fabricated on Nb:SrTiO₃ substrates by sol–gel process, and the influence of thermal processing details on the microstructure and ferroelectric property was investigated. Experimental results confirmed the different appearance of polycrystalline growth and epitaxial growth modes during the crystallization of KNN thin films. These two growth modes occurred under different thermal conditions within the narrow pyrolysis temperature scope ranging from 400°C to 500°C, respectively. By considering these findings, an optimizing combination between pyrolysis and annealing procedure was thought to be crucially important to obtain high‐performance KNN films with excellent crystallization state.     

Ferroelectric and piezoelectric properties of Ba0.85Ca0.15Ti0.90Zr0.10O3 films in 200 nm thickness range

Lead-free piezoelectric Ba_0.85Ca_0.15Ti_0.90Zr_0.10O₃ (BCZT) thin films were fabricated on Si/SiO₂/TiO₂/Pt (100) substrates following chemical solution deposition technique. Microstructure of the nano-sized BCZT particles crystallized in the thin film was thoroughly characterized. Ferroelectric, dielectric and piezoelectric properties of the films were investigated in detail. The BCZT films annealed at 800°C temperature exhibited high remanent polarization of 25 ± 1 μC/cm², energy density of 17 J/cm³, dielectric constant of 1550 ± 50 and dielectric tunability of 50%. Converse piezoelectric coefficients (d₃₃) obtained from piezo-response force microscopy (PFM) measurements on BCZT grains of different grain size (20-100 nm) distributed on the BCZT 700 film varied widely from 90 to 230 pm/V. The same for BCZT 800 measured on different grain size (30-130 nm) varied from 120 to 295 pm/V. These BCZT thin films with high dielectric, ferroelectric, and piezoelectric properties might be good alternative to the PZT films for thin film piezoelectric device applications.     

Full characterization for material constants of a promising KNN-based lead-free piezoelectric ceramic

Potassium-sodium niobate (K_1-xNa_xNbO₃, referred to as KNN) solid solutions, which are an important type of lead-free piezoelectric materials possessing environmentally friendly features, good piezoelectric response and high Curie temperature, have attracted considerable attention in replacing lead-based ceramics. In order to promote the application of KNN-based ceramics in piezoelectric devices, we characterized a complete set of material constants of a high performance KNN-based ceramic, that is 0.965(K_0.48Na_0.52) (Nb_0.96Sb_0.04)O₃-0.035Bi_0.5Na_0.5Zr_0.15Hf_0.75O₃ (KNNS-BNZH), whose Curie temperature is 235 °C, piezoelectric coefficient d₃₃ is 380 pC/N and electromechanical coupling factor k₃₃ is 70%. These results will benefit the design of piezoelectric transducers and actuators using lead-free piezoelectric ceramics.     

KNN-based piezoelectric ceramic multilayer actuators with Ni internal electrodes

On the road of lead-free piezoelectric ceramics into practical applications, the study of Ni-internal-electrode (K, Na)NbO₃-based (KNN-based) multilayer actuators (MLAs) is an important part, possessing the advantages of environmentally friendly and low cost. The Ni-internal-electrode KNN-based MLAs with different layer numbers and layer thicknesses were fabricated via the tape casting method and sintered in the reducing atmosphere. The piezoelectric layers consist of the main KNN-based phase and a trace amount of second phase Mn₄Nb₂O₉. The element diffusion between the Ni electrodes and KNN-based grains is tiny, indicating that Ni is suitable for co-firing with KNN-based ceramics. After sintering, the compressive stress perpendicular to the thickness direction and the “relative tensile stress” parallel to the thickness direction are retained in the MLAs, bringing influences on the piezoelectric and dielectric properties of KNN-based materials. Compared with the bulk ceramics, the prepared MLAs significantly reduce the driving voltages and increase the displacement outputs, which are more applicable to the scenarios of miniaturization and portability. Particularly, the 46-layer actuator shows high displacements of 1580 and 2737 nm under the voltages of 100 and 200 V, respectively. However, the inverse piezoelectric coefficient d₃₃* for each layer of MLAs is still lower than that of the bulk ceramics, indicating that the piezoelectric properties of the KNN-based materials are suppressed. To give full play to the piezoelectric properties of KNN-based materials, more attentions should be paid to the design of reasonable electrode structure and the development of internal electrode paste for MLAs.     

Effects of Heat‐Treatment Temperature on the Properties of (1–x)(Na0.5Bi0.5)TiO3–xBiAlO3 Lead‐Free Piezoelectric Thin Films

Lead‐free sodium bismuth titanate–aluminate bismuth [0.97(Na_0.5Bi_0.5)TiO₃–0.03BiAlO₃] solid‐solution films deposited on (100) Pt/TiO₂/SiO₂/Si substrates by a sol–gel process were pyrolyzed and annealed at different temperatures. The film annealed at 725°C with a pyrolysis temperature of 410°C exhibited the optimal electrical properties and excellent piezoelectric properties, with a remanent polarization 2P_r of 38 μC/cm² and a leakage current density of 10^?7–10^?6 A/cm² (E < 200 kV/cm). The values of the dielectric constant and dissipation factor at 100 kHz were 422 and 0.039, respectively. The piezoelectric coefficient of the film after poling at 168 kV/cm was found to be 57 pm/V, making the BNT‐BA films a viable lead‐free alternative to the lead‐based materials in such as biosensors and ultrasonic transducers.     

(Bi0.5Na0.5)ZrO3 modified KNN-based ceramics: Enhanced electrical properties and temperature insensitivity

To further improve the properties of KNN-based lead-free ceramics, a new ceramic system, (0.98-x)K_0.525Na_0.475Nb_0.965Sb_0.035O₃-0.02 BaZr_0.5Hf_0.5O₃-x(Bi_0.5Na_0.5)ZrO₃(KNNS-BZH-xBNZ) was designed, the relevant properties such as piezoelectricity, strain, and temperature stability were analysed in detail. It was found that the R-T phase boundary can be successfully constructed when x=0.030, and this two-phase coexistence shows relatively good comprehensive properties (d₃₃~410 pC/N, T_C~255 °C, S_uni~0.132%, and d₃₃*~441 pm/V). Meanwhile, its strain property also shows good temperature stability from room temperature to 180 °C (S_uni100°C/S_uniRT~97.5% and S_uni180°C/S_uniRT~83.9%), which is comparatively superior to many KNN-based ceramics and some lead-based ceramics. Therefore, KNNS-BZH-xBNZ ceramics may broaden the practical application of lead-free ceramics.     

Growth and electrical properties of high-Curie point rhombohedral Mn-Pb(In1/2Nb1/2)O3-Pb(Mg1/3Nb2/3)O3-PbTiO3 thin films

High-quality ternary relaxor ferroelectric (100)-oriented Mn-doped 0.36Pb(In_1/2Nb_1/2)O₃-0.36Pb(Mg_1/3Nb_2/3)O₃-0.28PbTiO₃ (Mn-PIMNT) thin films were grown on SrRuO₃-buffered SrTiO₃ single-crystal substrate in a wide deposition temperature range of 550-620°C using the pulsed laser deposition method. The phase structure, ferroelectric, dielectric, piezoelectric properties, and nanoscale domain evolution were studied. Under the deposition temperature of 620°C, the ferroelectric hysteresis loops and current-voltage curves showed that the film owned significantly enhanced remnant ferroelectric polarization of 34.5 μC/cm² and low leakage current density of 2.7 × 10⁻¹⁰ A/cm². Moreover fingerprint-type nanosized domain patterns with polydomain structures and well-defined macroscopic piezoelectric properties with a high normalized strain constant of 40 pm/V was obtained. Under in situ DC electric field, the domain evolution was investigated and 180° domain reversal was observed through piezoelectric force microscope. These global electrical properties make the current Mn-PIMNT thin films very promising in piezoelectric MEMS applications.     

Processing of 0.55(Ba0.9Ca0.1)TiO3-0.45Ba(Sn0.2Ti0.8)O3 lead-free ceramics with high piezoelectricity

We report a large piezoelectric constant (d₃₃), 720 pC/N and converse piezoelectric constant (d₃₃^*), 2215 pm/V for 0.55(Ba_0.9Ca_0.1)TiO₃-0.45Ba(Sn_0.2Ti_0.8)O₃ ceramics; the biggest value achieved for lead-free piezoceramics so far. The ceramic powders were calcined between 1050°C-1350°C and sintered at 1480°C. The best properties were obtained at a calcination temperature (CT) of 1350°C. The fitting combination of processing and microstructural parameters for example, initial powder particle size >2 µm, ceramics density ~95%, and grain size ~40 µm led to a formation of orthorhombic-tetragonal-pseudo-cubic (O-T-PC) mixed phase boundary near room temperature, supported by Raman spectra, pointed to the extremely high piezoelectric activity. These conditions significantly increase piezoelectric constants, together with high relative permittivity (ε_r) >5000 and a low loss tangent (tan δ) of 0.029. In addition, the d₃₃ value stabilizes in the range of 400-500 pC/N for all samples calcined between 1050°C and 1250°C. The results entail that the (Ba,Ca)(Sn,Ti)O₃ ceramics are strong contenders to be a substitute for lead-based materials for room temperature applications.     

The effect of calcium zirconate modifications on the microstructure and functional properties of sodium niobate thin films prepared by chemical solution deposition

Sodium niobate thin films doped with manganese (NN), and NN films modified with 5 or 10 mol % calcium zirconate (CZ) on platinized silicon substrates were prepared by chemical solution deposition. The 250-nm-thick films crystallize in a perovskite phase with fine, equiaxed grains. The NN films exhibit well-shaped ferroelectric loops with a remanent polarization and coercive field of ～10 μC/cm² and ～100 kV/cm, respectively. The modification with CZ strongly influences the ferroelectric response of the films: the remanent polarization progressively decreases to around 2.5 μC/cm². The absence of an anti-ferroelectric response, which has previously been confirmed in bulk NN-CZ ceramics, is attributed to the nanoscale microstructure and residual thermal stresses. All the studied films exhibit a piezoelectric response with the highest piezoelectric d₃₃ coefficient of 35 pm/V at 300 kV/cm bias field for the NN modified films with 5 mol % CZ, making them candidates for lead-free piezoelectric thin-film applications.     

Ink-jet printed BNT thin films with improved ferroelectric properties via annealing in wet air

In this work, an ink-jet printing process based on the sol-gel route was applied to prepare lead-free ferroelectric Na_0.5Bi_0.5TiO₃(BNT) thin films for the first time. Dense and crack-free films with perovskite structure were obtained from a modified precursor solution through multiple printing and pyrolysis processes. The ferroelectric, dielectric and electrical properties were significantly affected by the annealing temperature and atmosphere. The film annealed at 670?°C in wet air showed a high remnant polarization of 24.7?μC/cm² with a low coercive field of 263?kV/cm, the dielectric constant and loss were 185 and 0.1 at 10?kHz, respectively. It was found that wet air was an alternative to reduce oxygen vacancies and enhance properties of ferroelectric films, which can be explained by the defect chemical reaction between water and oxygen vacancies. X-ray photoelectron spectroscopy(XPS) confirmed the decrease of oxygen vacancies after annealing with water presence, with a formation of Ohmic conduction mechanism dominated by charged hydroxyl groups.     

High mechanical quality factor and piezoelectricity in potassium sodium niobate ceramics

Plenty of works have done to enhance the piezoelectricity of potassium-sodium niobate (KNN), aiming to replace lead-zirconate titanate (PZT) in the consideration of eco-friendly requirement. However so far, KNN ceramics with high piezoelectric performances tend to have a low mechanical quality factor (Q_m), which could result in excessive dielectric loss, especially when working in high frequencies. Thus, increasing Q_m is a crucial task in KNN-based ceramics. By constructing phase boundaries together with inducing oxygen vacancies, a new KNN ceramic system is built by using conventional solid-state method with high Q_m (>250), high piezoelectric performance as well as outstanding temperature stability. Optimum overall properties of KNN-based ceramics can be as large as d₃₃ = 231 pC/N, Q_m = 355, T_C = 366 °C. This work provides a deeper insight to KNN-based ceramics with high mechanical quality factor and makes a progress on the high frequency application of lead-free ceramics.     

Optical and Microwave Dielectric Properties of Phase Pure (K0.5Na0.5)NbO3 Thin Films Deposited by RF Magnetron Sputtering

(K_0.5Na_0.5)NbO₃ (KNN) thin films have been deposited onto Pt/Ti/SiO₂/Si and quartz substrates by RF magnetron sputtering. The films were deposited at 400°C with the variation in oxygen mixing percentage (OMP) ratio from 0% to 100% and annealed at 700°C in oxygen atmosphere. The crystallinity of the films is found to be increased with increased OMP. Dielectric properties of the films were examined over the frequency range from 1 kHz to 1 MHz and the temperature range of 30°C to 400°C. The Curie temperature of the films was found to be in the range 369°C–373°C. For the first time, the split postdielectric resonator (SPDR) method was used to measure the microwave (10–20 GHz) dielectric properties of KNN thin films. The optical properties of as‐deposited and annealed KNN thin films were investigated by means of transmittance spectra. The optical bandgap is calculated by using the Tauc relation, and found to be in the range 4.34–4.40 eV and 4.29–4.37 eV for the as‐deposited and annealed films, respectively. The refractive index (n_700nm) of the films found to be in the range 1.98–2.01 and 1.99–2.07 for as‐deposited and annealed films, respectively. The refractive index dispersion is analyzed by using Wemple–DiDomenico (W–D) single‐oscillator model. The effect of annealing and OMP on the refractive index, packing density and W–D parameters has been investigated. The average single oscillator energy (E_o) and dispersion energies (E_d) of the annealed KNN thin films are in the range of 6.17–7.16 eV and 18.77–22.19 eV, respectively. AC‐conductivity of the annealed films was analyzed by using double power law. Ag/KNN/Pt thin films followed the ohmic conduction (J ∝ E^α, where α ~1) and the low leakage current density obtained for the deposited at 100% O₂ is 3.14 × 10^?5 A/cm² at 50 kV/cm.     

Performance optimization of Mg-rich bismuth-magnesium-titanium thin films for energy storage applications

Due to advances in electronic device integration, miniaturization, and performance requirements, dielectric materials with a high energy storage density are required. Here, new BiMg_0.5Ti_0.5O₃ lead-free energy storage thin films with excess Mg (i.e., nominal BiMg_yTi_0.5O₃, with y = 0.50-0.62) were deposited on Pt/Ti/SiO₂/Si substrates by sol-gel and spin-coating methods. The introduction of excess Mg can obviously increase the dielectric breakdown strength of thin films due to the appearance of an amorphous phase. The maximum recoverable energy storage density increased from 26 J/cm³ at y = 0.50 to 44.1 J/cm³ at y = 0.56. Furthermore, the dielectric films exhibited excellent thermal stability of the energy storage density from 30 °C to 100 °C, indicating that bismuth-magnesium-titanium films are promising candidates for next-generation lead-free energy storage capacitor applications.     

Dielectric and ferroelectric properties of multilayer BaTiO3/NiFe2O4 thin films prepared by solution deposition technique

In this work different lead-free multilayered structures, composed of perovskite BaTiO₃ and spinel NiFe₂O₄ thin layers, were obtained by solution deposition method. Structural characterization of the sintered thin films confirmed the well-defined layered structure with overall thickness from 160 to 600 nm, crystalline nature of perovskite BaTiO₃ and spinel NiFe₂O₄ phases without secondary phases (after sintering below 900 °C) and grains on nanometer scale. Dielectric properties of the multiferroic multilayer BaTiO₃/NiFe₂O₄ thin films were analyzed in temperature and frequency range from 30 °C to 200 °C and 100 Hz to 1 MHz, respectively. In comparison to the pure BaTiO₃ films, the introduction of ferrite layer reduces dielectric response and increases low frequency permittivity dispersion of the multilayer thin films. The multilayer samples have shown relatively low dielectric loss with stronger contribution of conductivity at higher temperatures, and characteristic broad peak representing “relaxation” of the interface charge accumulation.     

Annealing temperature dependence of local piezoelectric response of (Pb,Ca)TiO3 ferroelectric thin films

In this work, we have systematically investigated the piezo/ferroelectric response of (Pb, Ca)TiO₃ thin films prepared by polymeric precursor method using simultaneously topography, piezoresponse force microscopy (PFM) and local piezoelectric hysteresis loop measurements. The thin films were grown on Pt/Ti/SiO₂/Si substrates and annealed at 400, 500 and 600 °C and subjected to structural characterization using x-ray diffraction, infrared and micro-Raman spectroscopy. The ferroelectric domains structure and the piezoelectric response evolved as a function of thermal annealing temperature as well as the density of active grains (number of switchable domains) progressively increased. Another important characteristic of these films is the onset of large area showing the coexistence of active (stronger piezoresponse signal) and inactive (weak or non piezoresponse signal) grains embedded in the polycrystalline perovskite matrix. A combination of out-of-plane (OP) and in-plane (IP) PFM images revealed local features of polarization component magnitudes in samples surface. Well-defined local piezoelectric hysteresis loop was achieved on top of individual nanometer-scale grains in both samples annealed at 500 and 600 °C, and the switching behavior is evident.     

Facile preparation of ferroelectric poly(vinylidene fluoride‐co‐trifluoroethylene) thick films by solution casting

We investigated the effects of annealing temperature and vacuum treatment on the crystallinity and ferroelectric properties of solution‐casted poly(vinylidenefluoride‐co‐trifluoroethylene), P(VDF‐TrFE), thick films. We varied the annealing temperature from 70°C to 150°C and achieved high‐quality ferroelectric thick films annealed at 130°C. Ferroelectric domains and their properties were confirmed using X‐ray diffraction, Fourier transform infrared spectroscopy with attenuated total reflection mode and ferroelectric/piezoelectric measurement systems. Drying and/or annealing in the vacuum allowed for the improvement of crystallinity and ferroelectric/piezoelectric properties. Importantly, the piezoelectric coefficient, d₃₃, of our optimal P(VDF‐TrFE) films after sufficient poling treatment was 36 pC/N and our P(VDF‐TrFE) power generator produced an output voltage of ～6 V under periodic bending and unbending motions. POLYM. ENG. SCI., 54:466–471, 2014. © 2013 Society of Plastics Engineers     

Photonic Sintering of Aerosol Jet Printed Lead Zirconate Titanate (PZT) Thick Films

Lead Zirconate Titanate (PZT) is a commonly used piezoelectric material due to its high piezoelectric response. We demonstrate a new method of printing and sintering micro‐scale PZT films with low substrate temperature increase. Self‐prepared PZT ink was Aerosol‐Jet printed on stainless steel substrates. After drying for 2 h in vacuum at 200°C, the printed PZT films were divided into two groups. The first group was traditionally sintered, using a thermal process at 1000°C for 1 h in an Argon environment. The second group was photonically sintered using repetitive sub‐msec pulses of high intensity broad spectrum light in an atmospheric environment. The highest measured substrate temperature during photonic sintering was 170.7°C, enabling processing on low melting point substrates. Ferroelectric measurements were performed with a low‐frequency sinusoidal signal. The remanent polarization (P_r) and coercive field (E_c) for thermally sintered PZT film were 17.1 μC/cm² and 6.3 kV/cm, respectively. The photonically sintered film had 32.4 μC/cm² P_r and 6.7 kV/cm E_c. After poling the samples with 20 kV/cm electric field for 2 h at 150°C, the piezoelectric voltage constant (g₃₃) was measured for the two film groups yielding ?16.9 × 10^?3 (V·m)·N^?1 (thermally sintered) and ?17.9 × 10^?3 (V·m)·N^?1 (photonically sintered). Both factors indicate the PZT films were successfully sintered using both methods, with the photonically sintered material exhibiting superior electrical properties. To further validate photonic sintering of PZT on low melting point substrates, the process and measurements were repeated using a polyethylene terephthalate (PET) substrate. The measured P_r and E_c were 23.1 μC/cm² and 5.1 kV/cm, respectively. The g₃₃ was ?17.3 × 10^?3 (V·m)·N^?1. Photonic sintering of thick film PZT directly on low melting point substrates eliminates the need for complex layer transfer processes often associated with flexible PZT transducers.     

Enhanced piezoelectric,electrocaloric and energy storage properties at high temperature in lead-free Bi0.5(Na1-xKx)0.5TiO3 ceramics

The piezoelectric, electrocaloric and energy storage properties were systemically investigated in lead-free Bi_0.5(Na_1-xK_x)_0.5TiO₃ ceramics from room temperature to high temperature region. These ceramics can be poled completely to obtain large piezoelectric coefficient (104–153 pC/N) at low electric field of ~30?kV/cm. The piezoelectric property shows good thermal stability due to high depolarization temperature (T_d). For BNKT₂₀, a large low electric field-induced strain of 0.36% is obtained at 120?°C under 50?kV/cm, the corresponding normalized strain coefficient is up to 720?pm/V, which is larger than other BNT-based ceramics at high temperature region. The electrocaloric properties of these ceramics are studied via indirect and direct methods. Large EC value (~1.08?K) in BNKT₂₀ ceramic is obtained at 50?kV/cm using indirect calculation. Above 100?°C, the dielectric energy storage density and efficiency of BNKT₂₀ is still up to ~0.85?J/cm³ and 0.75, respectively. The BNKT_x ceramics may become promising candidates in the fields of actuators, electrocaloric cooling and energy storage at high temperature region.     

Piezoelectric properties of (1-x)BZT-xBCT system for energy harvesting applications

In this study, we investigated (1-x)Ba(Zr_0.2Ti_0.8)O₃–x(Ba_0.7Ca_0.3)TiO₃ lead-free piezoelectric ceramics for energy harvester applications. The (1-x)BZT-xBCT ceramic is a promising lead-free piezoelectric material in the field of piezoelectric energy harvesting. Piezoelectric and energy properties of (1-x)BZT-xBCT ceramics were analyzed to confirm the possibility of using them as energy-harvesting materials. Especially, the vicinity of the phase convergence region was investigated to improve their piezoelectric properties. In the phase convergence region, cubic, rhombohedral, orthorhombic, and tetragonal regions co-exist within the narrow region. Near the phase transition region between the orthorhombic and tetragonal phase, the highest piezoelectric property d₃₃?=?464 pC/N and the highest energy density of 158.5 μJ/cm³ were observed. This output energy density of 158.5 μJ/cm³ is the recorded highest value among lead-free ceramics. We found that the optimal sintering temperature was 1475?°C and the optimal composition was BZT-0.5BCT.