Ferroelectric‒to‒relaxor crossover in KNN‒based lead‒free piezoceramics

This study investigated the phase transition behavior and electrical properties of (K_0.5Na_0.5)(Nb_1-xZr_x)O₃ (KNN?100xZ) and (K_0.5Na_0.5)NbO₃–yBaZrO₃ (KNN–100yBZ) lead–free piezoelectric ceramics. The phase transitions in crystal structures were compared in KNN ceramics between single Zr⁴⁺ doping and Ba²⁺Zr⁴⁺ co?doping. Piezoelectric properties such as the piezoelectric constant (d₃₃) and electromechanical coupling factor (k_p) are optimized for KNN?6BZ ceramics and were clarified via the polymorphic phase transition from the orthorhombic to pseudocubic phase. The fitted degree of diffuseness (γ) for a phase transition from the modified Curie–Weiss law indicated that KNN ceramics as ferroelectrics are gradually transformed through BaZrO₃ modification. Accordingly, the enhanced strain properties at y = 0.08 consist of coexisting ferroelectric domains and polar nanoregions that are supported by ferroelectric–to–relaxor crossover in KNN?100BZ ceramics.     

Room temperature constructing rhombohedral-tetragonal phase boundary in novel (Bi,Na)(Zr,Ti)O3 modified (K,Na)(Nb,Sb)O3 ceramics: Phase structure,defect and piezoelectric performance

Lead-free (1-x)(K_0.5Na_0.5)(Nb_0.96Sb_0.04)O₃-x(Bi_0.5Na_0.5)(Zr_0.8Ti_0.2)O₃ ceramics (abbreviated as (1-x)KNNS-xBNZT, x = 0, 0.01, 0.02, 0.03, 0.035 and 0.04) were synthesized by the solid-state method, and the dependence of phase evolution, microstructure, oxygen vacancy defect and electrical properties on compositions were carefully investigated. All ceramics had a pure perovskite structure and a dense microstructure. The phase transition temperatures (T_R-O and T_O-T) of the ceramics were adjusted by adding BNZT, and the rhombohedral-tetragonal (R-T) phase coexistence boundary was successfully constructed at room temperature when x = 0.03, the excellent piezoelectric performance (d₃₃ ～ 323 pC/N, k_p ～ 0.372) and high Curie temperature (T_C ～ 276 °C) have been achieved at this time. The grain size of the ceramics showed a strong difference on x content, and the maximum relative density value of 95.42% was obtained. The domain structure characterized by PFM confirmed that the ceramics possess small-sized nano-domains and complex domains at x = 0.03, which are the origin of enhanced piezoelectric properties. Moreover, the oxygen vacancy defect that can pin the domain walls was increased with the addition of (Bi_0.5Na_0.5)(Zr_0.8Ti_0.2)O₃. As a result, the doping with BNZT can significantly affect the phase structure and electrical properties of the ceramics, indicating that the (1-x)KNNS-xBNZT ceramics system with a R-T phase boundary is a promising lead-free piezoelectric material.     

A dispersed polycrystalline phase boundary constructed in CaZrO3 modified KNN based ceramics with both excellent piezoelectric properties and thermal stability

In this paper, the ceramics with composition of (0.98-x)(K_0.5Na_0.5)(Nb_0.96Sb_0.04)O₃-0.02(Bi_0.5Na_0.5)(Zr_0.8Ti_0.2)O_3-xCaZrO₃ (abbreviated as (0.98-x)KNNS-0.02BNZT-xCZ, x = 0, 0.01, 0.015, 0.02, 0.025, 0.03) were prepared by a traditional solid-state reaction method. The effect of the additional amount of CaZrO₃ on the phase structure, microstructure, dispersion index, domain structure and piezoelectric properties of ceramics was systematically studied. Finally, the piezoelectric properties and thermal stability of ceramics could be controlled by adding different amounts of CaZrO₃. The addition of CaZrO₃ transferred the phase structure of the ceramics from orthogonal-tetragonal (O-T) coexistence phase to rhombohedral-orthogonal (R–O) coexistence phase, which could be demonstrated by XRD test, temperature-dependent Raman spectra and ε_r‐T plot analysis. And when x = 0.02, the ceramics possessed the best piezoelectric and dielectric properties (d₃₃ = 253 pC/N, ε_r = 1185, tanδ = 0.044). Such excellent electrical properties could be originated from the heterogeneous domain structure and small-size nano-domains of the ceramics. Moreover, with the increase of CaZrO₃ doping amount, the dispersion index of ceramics gradually increased from 1.404 to 1.871, which showed more obvious dispersion phase transition characteristics and improved the thermal stability of ceramics. Particularly, when x = 0.02, after annealing at a high temperature of 220 °C (close to its Curie temperature), the d₃₃ tested at room temperature remained above 85% of that without annealing. The results indicated that (0.98-x)KNNS-0.02BNZT-xCZ ceramic was a promising lead-free piezoelectric ceramic system.     

Phase structure and enhanced piezoelectric properties in (1-x)(K0.48Na0.52)(Nb0.95Sb0.05)O3-x(Bi0.5Na0.42Li0.08)0.9Sr0.1ZrO3 lead-free piezoelectric ceramics

The piezoelectric properties of KNN lead-free piezoelectric ceramics could be greatly enhanced by forming multiphase coexistence. In this work, binary system (1-x)(K_0.48Na_0.52)(Nb_0.95Sb_0.05)O₃-x(Bi_0.5Na_0.42Li_0.08)_0.9Sr_0.1ZrO₃ [(abbreviated as (1-x)KNNS-xBNLSZ] ceramics with rhombohedral-tetragonal (r-T) phase boundary was designed and synthesized using the conventional solid-state sintering method, and effects of BNLSZ contents on their micrograph, phase structure and electrical properties were also investigated. According to phase diagram from the results of temperature-dependent capacitance and dielectric constant, the ceramics exhibit the R-T phase coexistence in the composition range of 3.5%≤x<4.5%, and an enhanced dielectric, ferroelectric, and piezoelectric behavior was obtained at such a phase boundary zone. As a result, the ceramics with x=0.04 exhibit optimum electrical properties of d₃₃~461 pC/N, k_p~46%, tan δ~0.03, P_r~16.9 μC/cm², and E_c ~9 kV/cm, together with a Curie temperature (T_C) of ~228 °C. Such a good comprehensive performance obtained in this present work is due to the R-T phase transition and enhanced ɛ_rP_r. It was believed that this ceramic system would promote the development of KNN-based lead-free ceramics.     

Dielectric,ferroelectric and field-induced strain behavior of K0.5Na0.5NbO3-modified Bi0.5(Na0.78K0.22)0.5TiO3 lead-free ceramics

Lead-free piezoelectric (1 ? x)Bi_0.5(Na_0.78K_0.22)_0.5TiO₃–xK_0.5Na_0.5NbO₃ (BNKT–xKNN, x = 0–0.10) ceramics were synthesized using a conventional, solid-state reaction method. The effect of KNN addition on BNKT ceramics was investigated through X-ray diffraction (XRD), dielectric, ferroelectric and electric field-induced strain characterizations. XRD revealed a pure perovskite phase with tetragonal symmetry in the studied composition range. As the KNN content increased, the depolarization temperature (T_d) as well as maximum dielectric constant (?_m) decreased. The addition of KNN destabilized the ferroelectric order of BNKT ceramics exhibiting a pinched-type hysteresis loop with low remnant polarization (11 μC/cm²) and small piezoelectric constant (27 pC/N) at 3 mol% KNN. As a result, at x = 0.03 a significant enhancement of 0.22% was observed in the electric field-induced strain, which corresponds to a normalized strain (S_max/E_max) of ～434 pm/V. This enhancement is attributed to the coexistence of ferroelectric and non-polar phases at room temperature.     

Achieving ultrabroad temperature stability range with high dielectric constant and superior energy storage density in KNN–based ceramic capacitors

Multilayer ceramic capacitors (MLCCs) had become an important component of many electronic devices on account of its miniaturization, high capacitance and reliability. To satisfy the requirements of MLCCs, the temperature–insensitivity and dielectric properties of the dielectric ceramics were urgent to be enhanced. In our work, (1–x)K_0.5Na_0.5NbO₃–xBi(Li_0.5Nb_0.5)O₃ (abbreviated to KNN–xBLN) were successfully synthesized by traditional solid state reaction method. On the one hand, the doping BLN induced the diffused phase transition and broadened the dielectric anomaly peaks, which improved the temperature insensitivity of KNN-based ceramics. On the other hand, the nanosized grains and dense microscopy boosted the breakdown electric field. Ultimately, the KNN–0.175BLN samples presented the excellent dielectric properties with high dielectric constant (1735) and low dielectric loss (1.9%) at room temperature with a wide temperature stability range (–62 – 300 °C), which exhibited the wider temperature stability range than X9R specification. Meanwhile, the x = 0.175 samples also achieved a high recoverable energy storage density of 3.71 J/cm³ under the breakdown electric field of 360 kV/cm. The designed KNN–based dielectric materials were expected to be applicable to the energy storage capacitor with standed high operating temperature.     

Textured (K0.5Na0.5)NbO3 ceramics prepared by screen-printing multilayer grain growth technique

The screen-printing multilayer grain growth (MLGG) technique is successfully applied to alkaline niobate lead-free piezoelectric ceramics. Highly textured (K_0.5Na_0.5)NbO₃ (KNN) ceramics with 〈0 0 1〉 orientation (f = 93%) were fabricated by MLGG technique with plate-like NaNbO₃ templates. The influence of sintering temperature on grain orientation and microstructure was studied. The textured KNN ceramics showed very high piezoelectric constant d₃₃ = 133 pC/N, and high electromechanical coupling factor k_p = 0.54. These properties were superior to those of conventional randomly oriented ceramics, and reach the level of those of textured KNN ceramic prepared by tape-casting technique. Compared with other grain orientation techniques, screen-printing is a simple, inexpensive and effective method to fabricate grain oriented lead-free piezoelectric ceramics.     

Enhanced electrical properties of the polymorphic phase boundary on the tetragonal side in K0.48Na0.52NbO3-based lead-free piezoelectric ceramics

Herein, (0.95?x)K_0.48Na_0.52NbO₃-0.05SrTiO₃-xCaZrO₃ piezoelectric ceramics were prepared using a conventional solid sintering process, and their microstructures, phase structures, and ferroelectric, dielectric, and strain properties were studied. The crystal structure of the ceramics changed from the coexistence of an orthogonal–tetragonal phase on the orthogonal side at x = 0 to that on the tetragonal side at x = 0.02 by improving the orthogonal–tetragonal transition temperature (～20 °C) with increasing CaZrO₃ (abbreviated as CZ) doping. A high electric field–induced strain of 0.33% with a Curie temperature of T_c = 256 °C was obtained at x = 0.02 and was approximately two times that observed at x = 0. The dielectric constant and maximum polarization were the highest at x = 0.02 in this (0.95?x)K_0.48Na_0.52NbO₃-0.05SrTiO₃-xCaZrO₃ system. These materials would be promising lead-free ceramics in the future.     

Room-temperature ferromagnetism in (K0.5Na0.5)NbO3-xBaNi0.5Nb0.5O3-δ ferroelectric ceramics with narrow bandgap

In this paper, a simple, reproducible and cost-effective solid-state reaction sintering process is developed to fabricate (K_0.5Na_0.5)NbO₃-xBaNi_0.5Nb_0.5O_3-δ (KNN-xBNN) ceramics with a narrow bandgap and room-temperature ferromagnetism. Here, we report a systematic investigation of the influence of the BaNi_0.5Nb_0.5O_3-δ (BNN) concentration on the properties of KNN-xBNN ceramics. All ceramics form orthorhombic perovskite structures with a space group Amm2 and a weak peak at the wavelength of 550 cm^?1 that is characteristic of the pillow shoulder of the orthorhombic phase. KNN-xBNN ceramics with x between 0.02 and 0.08 have a narrow bandgap of about 2.5 eV—much smaller than the 3.5 eV of its parent (K_0.5Na_0.5)NbO₃ (KNN) ceramic—which is attributed to Ni²⁺-oxygen vacancy combinations (Ni²⁺-V_O) raising the valence electron energy level of the KNN ceramic. Furthermore, doping BNN into KNN ceramics can significantly convert the magnetism from diamagnetism to ferromagnetism and the component of x = 0.08 achieves both maximum saturation magnetisation intensity (14 memu/g) and minimum coercive magnetic field (80 Oe). Our findings provide a systematic insight into the bandgap tunability and ferromagnetism induction at room temperature in lead-free perovskite KNN-xBNN ceramics, as well as demonstrate their potential applications in perovskite solar cells and multiferroic devices.     

Structural phase transitions and electrical properties of (KxNa1−x)NbO3-based ceramics modified with Mn

(K_0.5Na_0.5)NbO₃ (KNN) ceramics and KNN containing Li, Ta modified with 2 mol% of manganese have been produced using the mixed-oxide ceramics synthesis route. The structure and properties of these piezoelectric ceramics modified with manganese have been investigated using high resolution X-ray diffraction and electrical characterisation. The structural information about the ceramics was determined by Rietveld refinement with Fullprof. The phase transition temperatures observed with X-ray diffraction compares well with the values from dielectric studies. The addition of Mn slightly reduced the phase transition temperatures and for the sample containing only Li, the phase changed from orthorhombic to monoclinic phase with space group Pm. The dielectric, piezoelectric and ferroelectric properties of the samples decreased with Mn addition due to hard doping effects resulting from oxygen vacancies in the perovskite lattice.     

Improved ferroelectric,piezoelectric, and dielectric properties in pure KNN translucent ceramics by optimizing the normal sintering method

In this study, it is reported that various properties can be selectively derived in a pure (K_0.5Na_0.5)NbO₃, KNN ceramics through optimizing the sintering temperature by the conventional sintering method. High piezoelectric, ferroelectric, and dielectric properties such as d₃₃ = 127 pC/N, P_r = 31 μC/cm², and ε_r = 767 are obtained at the sintering temperature of 1100 °C. On the contrary, the specimen sintered at 1130 °C does not show high piezoelectric and ferroelectric properties, but it is translucent with a transmittance of 22% and 57% at the wavelength of 800 and 1600 nm respectively and shows a very high dielectric constant ε_r of 881. The origin of the high piezoelectric constant owes to large remanent polarization and dielectric constant, and dense microstructure with uniform distribution of large grains with the conjunction of relatively large crystal anisotropy. On the other hand, dense microstructure with almost no porosity, highly compacted grain boundaries, uniform distribution of grains, and relatively low crystalline anisotropy are responsible for the translucency and large dielectric constant of the ceramic specimens. This study demonstrates that the lead-free KNN ceramic has the potential to show multiple noteworthy properties such as piezoelectric, ferroelectric, dielectric, and transparent properties. This work provides a pure KNN ceramic simultaneously with high piezoelectric and transparent characteristics prepared only by using the conventional sintering method at a moderate sintering temperature for the first time in the literature.     

Phase transition,microstructure, and dielectric properties of Li/Ta/Sb co-doped (K,Na)NbO3 lead-free ceramics

Li/Ta/Sb co-doped lead-free (K_0.4425Na_0.52Li_0.0375)(Nb_0.93−xTa_xSb_0.07)O₃ (abbreviated KNLNST_x) piezoelectric ceramics, with Ta-doping ratio of x ranging from 0.0275 to 0.0675, were synthesized using the conventional solid-state reaction method at the sintering temperature of 1130 °C. The effects of Ta content on the microstructure, dielectric properties, and phase transition behavior of the prepared ceramics were systematically investigated. The X-ray diffraction results show that all KNLNST_x ceramics formed a secondary phase, which is assigned to the tetragonal tungsten-bronze type (TTB) structure phase, and showed a phase transition from an orthorhombic symmetry to a tetragonal symmetry across a composition region of 0.0375<x<0.0475. The grain shape and size that correspond to the phase structure transformations can be clearly observed in the scanning electron microscopy images. As x increased to 0.0475, the KNLNST_0.0475 ceramics changed from orthorhombic to tetragonal structure and showed excellent piezoelectric properties of d₃₃=313 pC/N, k_p=47%, and ε_r=1825. By contrast, samples of x=0.0375 with orthorhombic symmetry exhibited poor piezoelectric properties, with d₃₃=200 pC/N and ε_r=1015. These results indicate that phase structure is vital in the piezoelectric properties of KNN lead-free ceramics.     

Tetragonal tungsten bronze phase potential in increasing the piezoelectricity of sol-gel synthesized (K0.5Na0.5)1-xLixNbO3 ceramics

(K,Na)NbO₃ (KNN)-based ceramics have been proven to be formidable candidates among lead-free piezoelectric materials, yet poor reproducibility always hinders their progress. In the present study, the effects of low lithium substitution on the electrical properties and microstructure of (K_0.5Na_0.5)_1-xLi_xNbO₃ (KNLN) ceramics were investigated. All samples were synthesized by the sol-gel method. The Curie temperature (T_C) of the ceramics shifted to higher temperature and gradually decreased the monoclinic-tetragonal (T_M-T) phase transition. Li⁺ substitution had a prominent effect on the ferroelectric properties and improved the piezoelectric coefficient (d₃₃) up to 181 pC/N. X-Ray Diffraction (XRD) studies and Field Emission Scanning Electron Microscopy (FESEM) images revealed an inevitable tetragonal tungsten bronze (TTB) secondary phase, which was formed during the preparation process. It was demonstrated that the volatilization of Li⁺ cations facilitated TTB growth. The coexistence of two different phase structures proved to enhance the KNN piezoelectric performance.     

Low-temperature sintering and electrical properties of (K,Na)NbO3 based lead-free ceramics with high Curie temperature

Lead-free ceramics (1 ? x)(K_0.48Na_0.52)NbO₃–(x/5.15)K_2.9Li_1.95Nb_5.15O_15.3 (x = 0.3–0.6, KNN–KLN100x) were prepared by conventional sintering technique at a low temperature of 960 °C. The effects of KLN contents on microstructure, dielectric, and piezoelectric properties were investigated. After the addition of KLN, the sintering performance and Curie temperature of the ceramics were markedly improved. The ceramics with x = 0.3 exhibited very good piezoelectric properties: d₃₃ = 138 pC/N, k_p = 45.03%, T_c = 495 °C, the dielectric constant at room temperature ?_r (RT) = 478 and the maximum dielectric constant ?_r (max) = 5067. These results indicated that the KNN–KLN100x lead-free ceramics sintered at low temperatures are promising for high temperature piezoelectric applications.     

Effect of Li addition on phase formation behavior and electrical properties of (K0.5Na0.5)NbO3 lead free ceramics

In this work, Li-modified KNN ceramic compositions ((K_0.5Na_0.5)_1−xLi_x)NbO₃ with x = 0.03, 0.04, 0.05, 0.06, 0.65 and 0.07 were prepared by a conventional solid-state mixed-oxide method. The structural phase formation and microstructure were characterized by X-ray diffraction technique (XRD) and scanning electron microscopy (SEM). It has been found that a morphotropic phase boundary (MPB) between orthorhombic phase and tetragonal phases should exist between compositions with Li contents of 6-6.5%. The Curie temperature (T_c) of the ceramics shifted to higher temperature with increasing Li content. The room temperature dielectric constant was also seen to be higher than the pure KNN ceramics. In addition, the ferroelectric properties were found to enhance at near MPB compositions. This study clearly showed that the addition of Li could improve the dielectric and ferroelectric properties in (K_0.5Na_0.5)NbO₃ ceramics.     

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.     

Electrical and mechanical properties of BZT − xBCT lead-free piezoceramics

In this study, lead-free (1 − x)Ba(Zr_0.2Ti_0.8)O₃ − x(Ba_0.7Ca_0.3)TiO₃ compositions are synthesized via conventional solid oxide route, and the ceramics are fabricated with normal sintering in air. The effects of composition fluctuations on dielectric, piezoelectric, and mechanical properties are investigated. The phase structure and the microstructure are analyzed with X-ray diffraction and scanning electron microscopy. The best dielectric and piezoelectric properties of ε_r = 11 207 and d₃₃ = 330 pC/N were obtained for BZT−0.35BCT and BZT−0.5BCT ceramics, respectively. The mechanical behavior—in terms of Vickers hardness and compressive and flexural strengths—was investigated, and the best mechanical behavior was found in the vicinity of the phase transition boundary with x values between 0.5 and 0.6.     

Compositional inhomogeneity and segregation in (K0.5Na0.5)NbO3 ceramics

In this report, the effects of the calcination temperature of (K_0.5Na_0.5)NbO₃ (KNN) powder on the sintering and piezoelectric properties of KNN ceramics have been investigated. KNN powders are synthesized via the solid-state approach. Scanning electron microscopy and X-ray diffraction characterizations indicate that the incomplete reaction at 700 °C and 750 °C calcination results in the compositional inhomogeneity of the K-rich and Na-rich phases while the orthorhombic single phase is obtained after calcination at 900 °C. During the sintering, the presence of the liquid K-rich phase due to the lower melting point has a significant impact on the densification, the abnormal grain growth and the deteriorated piezoelectric properties. From the standpoint of piezoelectric properties, the optimal calcination temperature obtained for KNN ceramics calcined at this temperature is determined to be 800 °C, with piezoelectric constant d₃₃=128.3 pC/N, planar electromechanical coupling coefficient k_p=32.2%, mechanical quality factor Q_m=88, and dielectric loss tan δ=2.1%.     

Enhanced energy-storage properties and dielectric temperature stability of (Bi0·5Na0.5)0.84Sr0·16Ti1-x(Y0·5Nb0.5)xO3 lead-free ceramics

A series of lead-free (Bi_0·5Na_0.5)_0.84Sr_0·16Ti_1-x(Y_0·5Nb_0.5)_xO₃ (abbreviated as BNST-100xYN) relaxor ferroelectric ceramics were prepared by solid state reaction sintering. The micro morphology, dielectric properties, and energy storage properties of the ceramics with increasing doping content were systematically studied, and their conductive mechanism was also studied. The perovskite structure was not significantly changed with the addition of (Y_0·5Nb_0.5)⁴⁺ complex ions, but it led to a certain amount of flake grains appear and element precipitation with increasing composition. And the larger dielectric breakdown strength (DBS) and lower remanent polarization (P_r) were attained with the recoverable energy storage density (W_rec) of ~1.0433 J/cm³ for x = 0.04 composition. In addition, it showed outstanding dielectric temperature stability and cycle stability. These results indicated that BNST-4YN ceramics are an excellent candidate for energy storage device and temperature-stable dielectric equipment.     

Enhancing photostriction in KNN-based ceramics by constructing the morphotropic phase boundary and narrowing the energy band gap

Lead-free ferroelectric ceramics exhibiting photostriction effect has attracted a lot of attention in the past decade. Herein, we fabricated a series of (1?x)K_0.5Na_0.5NbO₃-x(La_0.51Na_0.49)(Zr_0.54Ni_0.46)O₃ ((1?x)KNN-xLNNZ) ceramics by traditional solid-state synthesis method aiming to improve photostriction. The addition of LNNZ in KNN has led to significant changes in phase structure and grain size. The ceramics with a composition of 0.97KNN-0.03LNNZ has shown a narrow bandgap ~2.43 eV, large piezoelectric coefficient (~209 pC/N), low dielectric loss (0.021 at 1 kHz) and high remnant polarization (~24 μC/cm²). Further, 0.97KNN-0.03LNNZ also exhibits a considerable photostrictive coefficient (~1.83 × 10^?9 m²W^?1), which is attributed to the combined effect of significantly narrow bandgap along with the morphotropic phase boundary. Further, all the substituted samples show distinct red shift of v1 mode compared to the pure KNN, which suggest a new kind of distortion introduced in (Nb, Zr, Ni)O₆ octahedron for KNN-based ceramics under variable power laser excitation. The obtained results indicate that LNNZ-substituted KNN ceramics can serve as a potential material for the fabrication of optomechanical devices.