Structural,electrical, magnetic and magnetoelectric properties of Co-doped BaTiO3 multiferroic ceramics

In this work, BaTi_1-xCo_xO₃ (BTCO) ceramics with x?=?0, 2.5, 5, 7.5 and 10?mol% have been synthesized and their structural, electrical, magnetic and magnetoelectric have been investigated. Rietveld refinement of XRD data reveals that pure BTO has pure tetragonal phase. On the other hand, between 2.5?≤?x?≤?7.5, BTCO shows both tetragonal as well as hexagonal phases. At x?=?10?mol%, BTCO shows only hexagonal phase. The grain size of the BTCO samples is found to increase with Co doping concentration. The ferroelectric polarization and relative permittivity of BTCO samples reduce with an increase in the Co concentration. A standard magnetization equation is used for fitting the magnetic hysteresis (M-H) curve, thus deconvoluting the ferromagnetic (FM) and paramagnetic (PM) components. The saturation magnetization (M_s) gradually increases from x?=?2.5 to x?=?10?mol%, the value being 0.8 memu/g and 8.92 memu/g respectively. The origin of magnetization is due to the oxygen vacancies and their associated exchange interaction. The magnetodielectric coefficient (MD) shows a reducing trend from 1.80 to 0.18 for x?=?2.5 to x?=?10?mol% respectively. The magnetoelectric coefficient $({\alpha }_{\mathit{ME}})$ for x?=?2.5?mol% is 3.399?mV/cm. Oe, while for x?=?10?mol% it is 0.896?mV/cm. Oe.     

Structure,electrical and dielectric properties of Ca substituted BaTiO3 ceramics

BaTi_1-xCa_xO_3-x [BTC100x] ceramics were synthesized via solid-state reaction method. Effect of Ca substitution on the structure, electrical and dielectric properties of BTC100x ceramics was systematically investigated. Calcined BTC100x powders were in tetragonal phase when x?≤?0.01, whereas transformed to cubic at x?>?0.01. Additionally, the diffraction peak (200) shifted to lower angles with increasing x, indicating increased unit cell volume. Meanwhile, Ba_0.97Ca_0.03TiO₃ [BC3T] ceramic was prepared and studied, to compare with BaTi_0.97Ca_0.03O_2.97 (BTC3). It was found that pure BaTiO₃ [BT] and BC3T ceramics had the similar structural and dielectric properties, whereas BTC3 ceramic showed much difference，XRD patterns, Raman spectrum, impedance spectra and dielectric-temperature spectra provided strong evidence of Ca²⁺ substitution at Ti site in BT lattice. Finally, BTC100x ceramics were produced and dielectric properties were investigated. With increasing x, the Curie temperature decreased from 128?°C (BT) to 42?°C (BTC5).     

Structural evolution and coexistence of ferroelectricity and antiferromagnetism in Fe,Nb co-doped BaTiO3 ceramics

Multiferroics are materials that exhibit two or more primary ferroic properties within the same phase and have potential applications in sensors, spintronics and memory devices. Here, the dielectric, ferroelectric and magnetic properties of novel multiferroics derived from BaTi_1?x(Fe_0.5Nb_0.5)_xO₃ (BTFN, 0.01 ≤ x ≤ 0.10) ceramics are investigated. Multiferroism in these ceramics is manifested by the coexistence of ferroelectric long-range ordering and antiferromagnetism. With increasing x-value, there is a structural evolution from a tetragonal perovskite to a mixture of tetragonal and cubic phases, accompanied by a decrease in the temperature of maximum permittivity. At room temperature, ferroelectric behaviour is evidenced by the presence of current peaks corresponding to domain switching in the current-electric field loops, while the observation of non-linear narrow magnetic hysteresis loops suggests dilute magnetism. The results indicate that in the x = 0.07 composition the antiferromagnetic order is established through an indirect super-exchange interaction between adjacent Fe ions.     

Effects of ionic radius on phase evolution in Ln-Al co-doped Ca1-xLnxZrTi2-xAlxO7 (Ln = La,Nd, Gd,Ho, Yb) solid solutions

Zirconolite ceramic has been considered as a promising matrix to dispose high-level radioactive waste due to its excellent performance in immobilizing radionuclides. In this work, a series of zirconate solid solutions with stoichiometric Ca_1-xLn_xZrTi_2-xAl_xO₇ (Ln = La, Nd, Gd, Ho, Yb; x?=?0.1–1) were systematically studied to investigate the radius effect on their phase evolution. Powder X-ray diffraction (XRD) and scanning electron microscopy with energy dispersive X-Ray spectrometry (SEM-EDX) were used to characterize the products. XRD and SEM results show that complete solid solutions of Ln and Al in zirconolite phase for Ca_1-xLn_xZrTi_2-xAl_xO₇ cannot found. In the Ca_1-xLa_xZrTi_2-xAl_xO₇ ceramics, single zirconolite phase cannot form, instead of multiple phases, such as zirconolite-2M, zirconia, perovskite and LaTi₂Al₉O₁₉. In the Nd-Al co-doping ceramics, nearly single zirconolite-2M and zirconolite-3O were found at x?≤?0.6 and 0.8?≤?x?≤?0.9, respectively. The miscibility gap between zirconolite-2M and 3O was found at x?=?0.7. Single zirconolite-2M formed in the Gd-Al, Ho-Al and Yb-Al co-doped ceramics can only be detected in a compositional range of 0.1?≤?x?≤?0.8. Higher incorporation contents in these three series can form an additional phase cubic zirconia which is usually a ceramic waste form for radionuclides. Based on the XRD data, lattice parameters of zirconolite-2M and zirconolite-3O were calculated by Pawley refinement method. The evolution of lattice parameters of zirconolite-2M shows great difference between different lanthanide ions, indicating different substitution mechanisms in the Ln-Al co-doped zirconolite-2M.     

Structural and thermoelectric properties of hydrothermal-processed Ag-doped Fe2O3

Fe_2-xAg_xO₃ (0?≤?x?≤?0.04) nanopowders with various Ag contents were synthesized at different hydrothermal reaction temperatures (150?°C and 180?°C). Their structural properties were fully investigated through an X-ray diffraction, a Fourier transform infrared spectroscopy, and an X-ray photoelectron spectroscopy. The hydrothermal reaction temperature, time, and Ag content remarkably affected the morphological characteristics and crystal structure of the synthesized powders. The Fe_2-xAg_xO₃ (0?≤?x?≤?0.04) powders synthesized at 150?°C for 6?h and the Fe_2-xAg_xO₃ (0.02?≤?x?≤?0.04) powders synthesized at 180?°C for 12?h formed the orthorhombic α-FeOOH phase with a rod-like morphology, whereas the Fe_2-xAg_xO₃ (0?≤?x?≤?0.01) powders synthesized at 180?°C for 12?h formed the rhombohedral α-Fe₂O₃ phase with a spherical-like morphology. The Fe_1.98Ag_0.02O₃ fabricated by utilizing Fe_1.98Ag_0.02O₃ powders synthesized at 180?°C showed the largest power factor (0.64?×10^?5 Wm^?1 K^?2) and dimensionless figure-of-merit (0.0036) at 800?°C.     

Effect of strontium substitution on the structure and dielectric properties of unfilled tungsten bronze Ba4-xSrxSmFe0.5Nb9.5O30 ceramics

The effects of Sr²⁺ substitution for Ba²⁺ on phase structure, microstructure, dielectric and electric properties for Ba_4-xSr_xSmFe_0.5Nb_9.5O₃₀ (x = 0, 1, 2, 3 and 4) ceramics were systematically researched. X-ray diffraction patterns show that Ba_4-xSr_xSmFe_0.5Nb_9.5O₃₀ (x = 0, 1, 2 and 3) ceramics are tetragonal tungsten bronze compound with a space group of P4bm, while the sample for x = 4 is an orthorhombic structure compound. The result can be corroborated by the analysis of Raman spectroscopy. As the Sr²⁺ contents increase from 0 to 3, the full width at half maximum of Raman lines of all samples increase gradually, indicating that the degree of lattice distortion increase. All tetragonal tungsten bronze ceramics exhibited a broad permittivity peaks, accompanied by frequency dispersion, indicating all samples are relaxor. The electrical properties of BSSFN ceramics were further studied by complex impedance spectroscopy. XPS spectrum shows that Fe²⁺ and Fe³⁺ coexist in Ba_4-xSr_xSmFe_0.5Nb_9.5O₃₀ ceramics, and their proportion varies with the concentration of Sr²⁺.     

Effect of Mn-doping on the structure and electrical properties of (Pb0.325Sr0.675)TiO3 ceramics

Pb_0.325Sr_0.675Ti_1-xMn_xO₃ ceramics (x?=?0, 0.001, 0.005, 0.01, and 0.05) were successfully prepared by traditional solid-state reaction method. It was found that the lattice constant calculated through Rietveld refinement initially increased and then decreased with increasing Mn content, which was attributed to the variation in valence state of Mn and Ti ions. The microstructure gradually varied from the coexistence of large grains and fine grains for x?=?0 to the uniform grain for x?=?0.05 by increasing the doping Mn ions. With increasing Mn content from x?=?0 to x?=?0.05, the Curie temperature (Tc) dramatically decreased from 25?°C to ??40?°C and dielectric maximum decreased from 27,100 to 13,200. Pb_0.325Sr_0.675Ti_1-xMn_xO₃ ceramics with x?=?0.001 showed the lowest dielectric loss of 0.006 with a relatively high dielectric peak value of ~ 21,000. The grain boundaries resistance obtained from the complex impedance decreased with the increase of Mn content. The decrease in resistance was ascribed to oxygen vacancies and electronics produced by the change of ionic valence state. X-ray photoemission spectroscopy revealed that Ti ions were Ti⁴⁺ and the valences of Mn ions were deduced to be mainly in the form of Mn²⁺ and/or Mn³⁺ for ceramics with low content of Mn, while the Ti ions were in the form of Ti³⁺ and Ti⁴⁺ and Mn ions were diverse valence states with the coexistence of Mn²⁺, Mn³⁺, and Mn⁴⁺ for ceramics with x?=?0.01 and 0.05.     

Dielectric and magnetic properties of (Pb,Ti) co-doped BiFeO3 multiferroic ceramics

In this study, Bi_0.9Pb_0.1Fe_1-xTi_xO₃ (0.05 ≤ x ≤ 0.20) multiferroic ceramics were prepared through solid-state reaction. The influence of Pb, Ti partial substitutions on the dielectric and magnetic properties of BiFeO₃ multiferroic ceramics was investigated and discussed in detail. X-ray diffractions confirm rhombohedral perovskite phase formation (R3c space group). Scanning electron microscopy (SEM) was employed to investigate the morphology, revealing a cuboidal microstructure with bimodal distribution of grain sizes. Magnetic studies were carried out and the results reveal a slight enhancement of saturation magnetization with Ti concentration increasing. The present data indicates that Bi_0.9Pb_0.1Fe_1-xTi_xO₃ can be used as multifunctional material in different magnetoelectric applications.     

Bond ionicity,lattice energy,bond energy,and microwave dielectric properties of Ca1-xSrxWO4 ceramics

The Ca_1-xSr_xWO₄ (x?=?0, 0.02, 0.04, 0.06, 0.08, 0.10) ceramics were fabricated through solid-state reaction, and the relationships among microwave dielectric properties of Ca_1-xSr_xWO₄, bond ionicity, lattice energy and bond energy were systematically investigated for the first time. The patterns of X-ray diffractions of Ca_1-xSr_xWO₄ presented tetragonal scheelite structure and no second phase appeared throughout the entire compositions. Dielectric properties of Ca_1-xSr_xWO₄ were proved to be related to the microstructures: dielectric constant (ε_r) of Ca_1-xSr_xWO₄ was dependent on the bond ionicity; the quality factor (Q×f₀) of Ca_1-xSr_xWO₄ was affected by W-site lattice energy when intrinsic loss is dominant; the temperature coefficient of resonant frequency (|τ_f|) would increase if B-site bond energy decreased. Ca_1-xSr_xWO₄ ceramic showed excellent microwave dielectric properties, ε_r =?9.42, Q×f₀ =?79876?GHz and τ_f =??18.8?ppm/°C when x?=?0.08 and sintered at 1100?°C for 4?h.     

Influence of the Spark Plasma Sintering temperature on the structure and dielectric properties of BaTi(1-x)ZrxO3 ceramics

In this work, structural and dielectric properties of BaTi_(1-x)Zr_xO₃ (BTZ) ceramics prepared by Spark Plasma Sintering (SPS) from powders obtained via Self-propagating High-temperature Synthesis (SHS) are shown to be strongly affected by the sintering temperature. In addition, a post-annealing treatment in air of the as-prepared ceramics leads to a transition from the hexagonal to the tetragonal and cubic phases. The SPS ceramics corresponding to compositions 0.05 ≤ x ≤ 0.20 and obtained at a sintering temperature of 1200 °C exhibit a standard ferroelectric behavior. In contrast, a diffuse phase transition is observed for the case of ceramics sintered at higher temperatures. Finally, the BTZ ceramic containing 5 at.% of Zr displays the best dielectric permittivity and piezoelectric properties as compared to the other compositions taken into account.     

Negative magnetization and exchange bias effect in Fe-doped CoCr2O4

Polycrystalline ceramics of Co(Cr_1-xFe_x)₂O₄ (0?≤?x?≤?0.12) were experimentally studied based on a series of temperature and time-dependent dc magnetic measurements using different magnetic field histories. Magnetization in field cooling process was continuously decreased for doping content x in the range of 0?≤?x?≤?0.04. Remarkable negative magnetization is observed when x reaches to 0.06 and persists up to x?=?0.1. Two-sublattice model is established and competition of the two magnetic sublattices is responsible for the phenomenon. The magnetic switching effect is realized just by changing the magnitude of the applied magnetic field and double magnetocaloric effects are obtained. These unique features under low magnetic fields show attractive for application in spintronic devices due to that the magnetic state can effectively be tuned through magnetic field or temperature. Besides, the system exhibits both positive and negative exchange bias fields which are considered to be originating from the unidirectional anisotropy of exchange coupling of antiferromagnetic/ferromagnetic phases and spin reorientation of the two sublattices magnetic moments, respectively.     

Structural,electrical, magnetic and magnetoelectric properties of Fe doped BaTiO3 ceramics

In the present work structural, electrical, magnetic and magnetodielectric properties of BaTi_1−xFe_xO₃ (0%≤x≤10%) ceramics have been investigated. X-ray diffraction (XRD) study reveals that the coexistence of tetragonal and hexagonal phases is strongly influenced by Fe doping concentration. The increase in Fe-doping content leads to the development of hexagonal phase along with an increase in average grain size. A reduction in the dielectric properties is also observed. All BaTi_1−xFe_xO₃ (BTFO) compositions exhibit ferroelectric behavior at room temperature. Remnant polarization (P_r) for pure BaTiO₃ (BTO) has been found to be 7.50 µC/cm² and further decreases with an increase in the Fe concentration. All Fe doped samples exhibit ferromagnetic ordering with saturation magnetization (M_s) being 26 memu/g for x=2.5%. Further, at x=5%, it decreases and thereafter again increases with Fe concentration. The magnetodielectric coefficient increases with Fe doping concentration and highest value found to be 2.80 at x=2.5%.     

Structure and electrical properties of Ca2+-doped (Na0.47Bi0.47Ba0.06)TiO3 lead-free piezoelectric ceramics

The lead-free piezoelectric ceramics (Na_.47Bi_.47Ba_.06)_1-xCa_xTiO₃ (x?=?0, 0.01, 0.02, 0.03, 0.05, and 0.08, abbreviated as BNBTC/0, BNBTC/1, BNBTC/2, BNBTC/3, BNBTC/5, and BNBTC/8, respectively) were obtained using the solid-state reaction method. The structure, electric conductivity, and dielectric, ferroelectric, and piezoelectric properties of the Ca²⁺-doped (Na_.47Bi_.47Ba_.06)TiO₃ ceramics were thoroughly investigated. The ceramics sintered at 1200?°C exhibit dense microstructures, having relative densities higher than 96%. The X-ray diffraction results demonstrate that all ceramics have a pure perovskite structure. The mean grain sizes of the ceramics are related to the Ca²⁺ quantity. A small quantity of Ca²⁺ ions (x?≤?0.03) improves the piezoelectric and ferroelectric properties of the samples. The dielectric behavior of the samples is sensitive to the Ca²⁺ content and electric poling. The results demonstrate that the electrical properties of the (Na_.47Bi_.47Ba_.06)TiO₃ lead-free ceramics can be well tuned by varying the Ca²⁺ quantity.     

Colossal permittivity and dielectric relaxations in Tl + Nb co-doped TiO2 ceramics

A series of Tl?+?Nb co-doped TiO₂ ceramics ((Tl_0.5Nb_0.5)_x%Ti_1-x%O₂ 0.5?≤?x?≤?10.0) were prepared by a solid-state reaction method under N₂ atmosphere. The evolution of their microstructures, and dielectric properties were systematically studied. The co-doped ceramics exhibited a tetragonal rutile structure wherein the Nb and Tl elements were homogeneously distributed. The cell volumes, grain size, and permittivity increased with doping x, whereas the impedance values of the grain and grain boundary decreased with an increasing x. The optimum dielectric performance (ε_r >?10⁴, tanδ?<?0.05) in the range of 10–10⁶ Hz was obtained for x?=?1.5 with a corresponding grain boundary active energy of 0.86?eV. Four types of dielectric relaxation were observed at different temperature ranges: 10–30?K, 30–200?K, 200–350?K and 350–475?K; those dielectric relaxtions were respectively caused by electron-pinned defect-dipoles, electron hopping, oxygen vacancy hopping, and Maxwell–Wagner polarization. The colossal permittivity is primarily a result of the electron-pinned defect-dipole polarization.     

Dielectric properties of Sm, Nd and Fe doped Bi1.5Zn0.92Nb1.5O6.92 pyrochlores

New pyrochlore ceramics have been produced by doping Sm and Nd into the Bi site and Fe into the Nb site in the Bi_1.5Zn_0.92Nb_1.5O_6.92 (BZN) pyrochlore. Doped pyrochlore ceramics were produced by conventional solid state mixing of oxides at different doping levels using the compositions of Bi_1.5−xSm_xZn_0.92Nb_1.5O_6.92, Bi_1.5−xNd_xZn_0.92Nb_1.5O_6.92 and Bi_1.5Zn_0.92Nb_1.5−xFe_xO_6.92−x. The solubility limit of cations was determined as x = 0.13, 0.18 and 0.15 for Sm, Nd and Fe, respectively. While Sm and Nd increased the dielectric constant (?), Fe doping led a decrease in ?. Dielectric constant of Sm and Nd doped BZN increased to 199 at x = 0.13 (Sm) and to 219 at x = 0.18 (Nd). At low Fe dopings (x = 0.05), the dielectric constant of BZN increased to 242 but decreased to 211 at x = 0.15. The dielectric losses were lower for Sm and Nd dopings than Fe but in all cases it was lower than 0.006. The dielectric constant of Sm, Nd and Fe doped BZN ceramics was nearly independent of frequency within the frequency range between 1 kHz and 2 MHz, but decreased considerably with temperature between 20 and 200 °C. Temperature coefficient of Sm doped BZN (−354 ppm/°C) was lower than Nd and Fe doped BZN ceramics at solubility limits (−538 ppm/°C for Nd and −565 ppm/°C for Fe).     

Dielectric,magnetic and magnetoelectric properties of Ni0.5Zn0.5Fe2O4+Pb(Zr0.48Ti0.52)O3 composite ceramics

Magnetoelectric composite ceramics of spinel ferrite Ni_0.5Zn_0.5Fe₂O₄ (NZFO) with high magnetic permeability and tetragonal perovskite Pb(Zr_0.48Ti_0.52)O₃ (PZT) with high piezoelectric constant were synthesized by common solid state reaction method. XRD and SEM showed that high dense composite ceramics without any foreign phases were obtained. The ceramics showed excellent dielectric and magnetic properties, which were stable in a large frequency range. The dielectric peak became wider with the ferrite content in the permittivity spectrum with temperature. With the increase in the ferrite content, the magnetic Curie temperature shifted to higher temperature and closed to that of the pure ferrite. In addition, the magnetoelectric coefficient enhanced as the increase in the ferrite content. The properties of the composite ceramics could be adjusted by the ferrite content. These research results provided a powerful experimental basis for the sensor and transducer in microelectronic and microwave devices.     

Enhanced ferroelectric properties in (Ba1−xCax)(Ti0.94Sn0.06)O3 lead-free ceramics

Lead-free (Ba_1−xCa_x)(Ti_0.94Sn_0.06)O₃ (BCST) (x = 0.01-0.04) ceramics were prepared using a solid-state reaction technique. The effects of Ca content on the phase structure and electrical properties of the BCST ceramics were investigated. High piezoelectric coefficient of d₃₃ = 440 pC/N, planar electromechanical coupling factor of k_p = 45% and dielectric constant ?_r = 6900 were obtained for the samples at x = 0.03. At room temperature, a polymorphic phase transition (PPT) from orthorhombic phase to tetragonal phase was identified in the composition range of 0.02 < x < 0.04.     

Large electrocaloric effect in lead-free Ba1-xCaxTi1-yZryO3 ceramics under strong electric field at room-temperature

In this study, lead-free Ba_1-xCa_xZr_yTi_1-yO₃ (BCTZ(x, y)) ceramics were prepared by means of the classic solid-state reaction method. The morphotropic phase transition (MPB) from the orthorhombic to the tetragonal phase (O-T) was identified in this composition. Besides, the identification of those two structures at room temperature (RT) was made possible thanks to an X-ray diffraction (XRD) study. In order to determine the phase transitions dielectric measurements were conducted. Based on Maxwell equation, the electrocaloric (EC) effect in the studied ceramics was performed via the indirect method. The compositions gave maximum EC temperature changes (ΔT) at above their T_C on application of a 3?kV/mm electric field. These temperature changes are ΔT?=?0.565?K at T_EC=?392?K, ΔT?=?0.548?K at T_EC=?365?K and ΔT?=?0.235?K at T_EC=?307?K for BCZT(10%,5%), BCZT(13%,10%) and BCZT(20%,15%), respectively. At RT, these compositions provided a very interesting EC coefficient (ξ?=?ΔT/ΔE) compared to the pure BaTiO₃ (BT). These values, lying between 0.105 Kmm/kV and 0.188Kmm/kV for ΔE?=?3?kV/mm, are also greater than those related to some lead-based ferroelectric.     

Structure,dielectric and piezoelectric properties of Ba0.90Ca0.10Ti1−xSnxO3 lead-free ceramics

Lead-free piezoelectric ceramics Ba_0.90Ca_0.10Ti_1−xSn_xO₃ have been prepared by a conventional ceramic fabrication technique and the effects of Sn⁴⁺ on the structure, dielectric and piezoelectric properties of the ceramics have been investigated. All the ceramics exhibit a pure perovskite structure. After the substitution of Sn⁴⁺, the crystal structure of ceramics is transformed gradually from a tetragonal to an orthorhombic phase, and becomes a pseudo-cubic phase at x≥0.14. The substitution also decreases the Curie temperature greatly from 138 °C at x=0 to 33 °C at x=0.12, and shifts the orthorhombic–tetragonal phase transition to higher temperatures. Coexistence of the orthorhombic and tetragonal phases is formed in the ceramic at x=0.10, leading to significant improvements in the piezoelectric properties: d₃₃=521 pC/N and k_p=45.5%. Our results also reveal that the ceramics sintered at higher temperatures contain larger grains, and thus exhibit more noticeable tetragonal–orthorhombic phase transition and enhanced ferroelectric and piezoelectric properties.     

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.