Growth of (Na0.5K0.5)NbO3 single crystals by abnormal grain growth method from special shaped nano-powders

Using the composite powders of (Na_0.5K_0.5)NbO₃ (NKN) nano-particles and nano-rods as starting materials, the NKN single crystals were prepared by abnormal grain growth (AGG) method. The morphology evolution and the formation mechanism in the crystal growth process were investigated in detail. The results revealed that the average size and the apparent quantity of abnormal grains increased gradually with the increase of sintering temperature. The biggest NKN single crystals with size of about 3 mm were obtained at 950 °C for 2 h. Though the nano-particles and nano-rods have the same composition, the driving forces are distinctively different due to the diversity of grain morphology. The nano-rods have the large driving forces especially at high sintering temperature, which plays a dominant role in facilitating the formation of NKN single crystals during AGG process.     

Thermal stability and local atomic structure of (Na0.5K0.5)NbO3 doped BaTiO3 ceramics

Dielectric properties of x(Na_0.5K_0.5)NbO₃–(1−x)BaTiO₃ (x=0.00 and 0.06) specimens were investigated in terms of changes in local atomic structure, according to the phase transition by elevating the overall temperature. A 0.06(Na_0.5K_0.5)NbO₃–0.94BaTiO₃ (NKN–BT) specimen exhibited enhanced temperature stability along with an increased dielectric constant. The degree of reduction in tetragonality (c/a) at the Curie temperature was smaller in NKN–BT compared to that in pure BaTiO₃, as calculated by Rietveld refinement. From a comparison of the pre-edge region in the Ti K-edge, it was determined that the off-center displacement of the Ti atom was also raised to 13.4% through NKN substitution, with a change in local orientation from the [001] to the [111] directions. The substitution by NKN, which has a different ionic radius and electrical charge compared with BaTiO₃, causes structural distortion of the TiO₆ octahedra in the NKN–BT lattice, resulting in local polarization. These structural changes lead to the temperature stability of the dielectric constant and an overall improvement in the electrical properties of BaTiO₃.     

High‐Performance (Na0.5K0.5)NbO3 Thin Film Piezoelectric Energy Harvester

The pseudocubic structure of a (Na_0.5K_0.5)NbO₃ (NKN) film grown on a Pt/Ti/SiO₂/Si substrate changed to an orthorhombic structure when the film was transferred onto a polyimide substrate. Piezoelectric constant for the transferred NKN film increased considerably from 74 ± 11 to 120 ± 18 pm/V because the crystal structure of the film had changed from pseudocubic to orthorhombic. A gold interdigitated electrode was deposited onto the transferred NKN film to synthesize a NKN piezoelectric energy harvester. The NKN piezoelectric energy harvester was poled before bending under a 100 kV/cm DC electric field across the electrodes. When a strain of 0.85% and a strain rate of 4.05%/s were applied to the NKN piezoelectric energy harvester, it produced a maximum output voltage of 1.9 V and a current of 38 nA, corresponding to a power density of 2.89 μW/cm³.     

Effects of sintering aid and atmosphere powder on the growth of (K0.5Na0.5)NbO3 single crystals fabricated by solid-state crystal growth method

(K_0.5Na_0.5)NbO₃ (KNN) + x (= 1, 0.5, 0.05, and 0) wt%Co₃O₄ single crystals were fabricated by a solid-state crystal growth method with a KTaO₃ seed crystal and a KNN atmosphere powder, and the effects of the sintering aid content x and the addition of Co₃O₄ to the atmosphere powder on the growth of the single crystals were investigated. The formation of pores in the single crystals was suppressed by a decrease of x, which, however, decreased the crystal growth length. On the other hand, dense and large KNN single crystals could be fabricated by sintering with a KNN + 5 wt%Co₃O₄ atmosphere at x = 0. The dielectric, ferroelectric, and piezoelectric properties of the KNN single crystals were comparable to those of reported (K,Na)NbO₃ single crystals. These results would be useful for fabricating dense and large single crystals by the solid-state crystal growth method.     

Effect of monovalent ions on the piezoelectric properties of (Na0.5K0.5)NbO3–(M)TaO3 ceramics

Sodium potassium niobate (NKN) ceramics modified by lithium or silver tantalates were prepared in order to compare the effect of monovalent additives and then their crystal structure, sinterability, and dielectric and piezoelectric properties were investigated with varying the amount of additives. It was clearly seen for the silver tantalate added NKN ceramics that dielectric constant, k_p and d₃₃ were dependent on the density and microstructure. While NKN ceramics added with lithium tantalate exhibited strong dependence on the existence of morphotrophic phase boundary and second phase formation rather than the density. These results were explained in terms of the phase formed and microstructure and sinterability.     

Piezoelectric K0.5Na0.5NbO3 Ceramics Textured Using Needlelike K0.5Na0.5NbO3 Templates

Improved performance by texturing has become attractive in the field of lead‐free ferroelectrics, but the effect depends heavily on the degree of texture, type of preferred orientation, and whether the material is a rotator or extender ferroelectric. Here, we report on successful texturing of K_0.5Na_0.5NbO₃ (KNN) ceramics by alignment of needlelike KNN templates in a matrix of KNN powder using tape casting. Homotemplated grain growth of the needles was confirmed during sintering, resulting in a high degree of texture parallel to the tape casting direction (TCD) and the aligned needles. The texture significantly improved the piezoelectric response parallel to the tape cast direction, corresponding to the direction of the strongest <001>_pc orientation, while the response normal to the tape cast plane was lower than for a nontextured KNN. In situ X‐ray diffraction during electric field application revealed that non‐180° domain reorientation was enhanced by an order of magnitude in the TCD, compared to the direction normal to the tape cast plane and in the nontextured ceramic. The effect of texture in KNN is discussed with respect to possible rotator ferroelectric properties of KNN.     

Enhanced piezoelectric property in Mn-doped K0.5Na0.5NbO3 ceramics via cold sintering process and KMnO4 solution

Through mixing the KMnO₄ solution with K_0.5Na_0.5NbO₃ (KNN) powders, cold sintering process (CSP) was employed to fabricate high-density Mn-doped KNN green pellets and ceramics. The microstructure, doping effect of Mn and electrical properties of these ceramics were studied in detail. Compared with conventional sintering (CS), the CSP supports the homogeneity of dopants and then promotes grain growth and ceramic densification; thus the Mn-doped KNN ceramics prepared by CSP show the obviously higher density and larger grain size. Besides, the less alkalis volatilization and oxygen vacancies result in more Mn³⁺ but less Mn⁴⁺ in CSP ceramics compared to CS ones, which endows the pinning effect and good poling characteristics in CSP ceramics. All the previous results contribute to the high dielectric constant and remnant polarization in CSP ceramics, which support the enhanced piezoelectric coefficient and are much superior than Mn-doped KNN ceramics prepared by CS. This work reveals that CSP can be a new doping strategy to perform chemical modification of electrical properties in KNN ceramics.     

Optical dispersion and bandgap of pure and Mn-doped 0.92Na0.5Bi0.5TiO3-0.08K0.5Bi0.5TiO3 lead-free single crystals

Optical properties of lead-free ferroelectric pure and Mn-doped 0.92Na_0.5Bi_0.5TiO₃-0.08K_0.5Bi_0.5TiO₃ (NBT-8KBT) single crystals have been investigated systematically. Refractive index and extinction coefficient were measured and the critical parameters are obtained by modified Sellmeier dispersion equations and single-oscillator dispersion relation. The decline of refractive index for Mn:NBT-8KBT could be related to the lattice distortion of the Mn ions doping. High transmittance (>70%) over the transparent region (>400 nm) was found in the pure NBT-8KBT, higher than that of Mn:NBT-8KBT, which could be caused by the increase of domain wall density. An about 100 nm red-shift of absorption edge was observed in the Mn:NBT-8KBT single crystal, which is located in the visible region. Optical bandgap energies calculated through Tauc equation and a large bandgap difference of 2.96 and 2.62 eV occurs in the NBT-8KBT and Mn:NBT-8KBT, respectively, which illustrates the modulation of the band structures by Mn doping.     

Piezoelectric enhancements in K0.5Na0.5NbO3-based ceramics via structural evolutions

The current work aims to compare the effect of systematic A-site and B-site substitutions on the piezoelectricity of Ka_0.5Na_0.5NbO₃ (KNN)-based perovskite ceramics. The A-site elements was replaced by Li⁺ while Nb5⁺ was substituted by Sb⁵⁺ to form (K_0.4675Na_0.4675Li_0.065)NbO₃ (KNLN) and (K_0.4675Na_0.4675Li_0.065)(Nb_0.96Sb_0.04)O₃ (KNLNS) respectively. The ceramics were prepared using solid-state sintering method. The density of the ceramics steadily improved with the substitutions while the crystal structure evolved from monoclinic (in KNN) to the coexistence of monoclinic and tetragonal (in KNLN) and finally tetragonal in KNLNS. Distinct variations on size and morphology were recorded. Although density, crystal structure and morphology have minor effect on the E_c, they imposed considerable influences on P_r, d₃₃ and k_p. Despite relatively lower density, KNLN exhibited the highest P_r, d₃₃ and k_p at 9.80 μC/cm²,185 pC/N and 0.43 respectively signifying the positive enhancement brought by the co-existence of monoclinic and tetragonal crystal structures. More importantly, this work systematically proved that the co-existence of both structures signified the morphotropic phase boundary (MPB) composition as the primary factor for the enhancement of KNN piezoelectric properties.     

High performance lead-free piezoelectric 0.96(K0.48Na0.52)NbO3-0.03[Bi0.5(Na0.7K0.2Li0.1)0.5]ZrO3-0.01(Bi0.5Na0.5)TiO3 single crystals grown by solid state crystal growth and their phase relations

0.96(K_0.48Na_0.52)NbO₃-0.03[Bi_0.5(Na_0.7K_0.2Li_0.1)_0.5]ZrO₃-0.01(Bi_0.5Na_0.5)TiO₃ single crystals were grown for the first time by the solid state crystal growth method, using [001] or [110]-oriented KTaO₃ seed crystals. The grown single crystal shows a dielectric constant of 2720 and polarization-electric field loops of a lossy normal ferroelectric, with P_r = 45 μC/cm² and E_c = 14.9 kV/cm, while the polycrystalline samples with a dielectric constant of 828 were too leaky for P-E measurement due to humidity effects. The single crystal has orthorhombic symmetry at room temperature. Dielectric permittivity peaks at 26 °C and 311 °C, respectively, are attributed to rhombohedral-orthorhombic and tetragonal–cubic phase transitions. Additionally, Raman scattering shows the presence of an orthorhombic-tetragonal phase transition at ∼150 °C, which is not indicated in the permittivity curves but by the loss tangent anomalies. A transition around 700 °C in the high temperature dc conductivity is suggested to be a ferroelastic-paraelastic transition.     

Improved ferroelectric photovoltaic effect in Mn-doped lead-free K0.5Na0.5NbO3 films

The pure and Mn-doped K_0.5Na_0.5NbO₃ (KNN) films were deposited using solution-gelation method. The crystal structure, ferroelectric properties, spectral response and J-V performance of photovoltaic effect were systematically investigated. Both the ferroelectric and leakage properties are obviously enhanced for Mn-doped KNN films. A fascinating phenomenon is observed that the ferroelectric photovoltaic effect is enhanced in Mn-doped KNN films, which is originated from the improved ferroelectric polarization and narrower band gap. The transition element Nb partially substituted by Mn results in the lattice distortion and further destroys the symmetry space structure, which enhances ferroelectric polarization. And the narrower band gap effectively decreases the internal potential barrier to separate the carriers. This work gives a clear relationship between the lattice distortion, ferroelectric and photovoltaic response. It is certain that lead-free transparent K_0.5Na_0.5NbO₃ films can be potentially applied in viable ferroelectric based solar cells.     

Electrical Properties of a 0.95(Na0.5K0.5)NbO3–0.05CaTiO3 Thin Film Grown on a Pt/Ti/SiO2/Si Substrate

An amorphous phase was formed in a 0.95(Na_0.5K_0.5)NbO₃–0.05CaTiO₃ (NKN‐CT) film grown at 300°C, and a low‐temperature transient Ca₂Nb₂O₇ phase was formed in the film grown at 500°C. In films grown at high temperatures (≥600°C), secondary phases such as K_5.75Nb_10.85O₃₀ and K₄Ti₁₀Nb₂O₂₇ were developed without the formation of a NKN‐CT phase, probably because of Na₂O evaporation. The same secondary phases were formed in the film grown at 300°C and subsequently annealed at 850°C under an air atmosphere. However, a homogeneous NKN‐CT phase was formed in films grown at 300°C and subsequently annealed at 830°C–880°C under the K₂O and Na₂O atmospheres. Moreover, the film annealed at 830°C in particular exhibited good electric and piezoelectric properties, including a high dielectric constant of 747 with a low dissipation factor of 0.93% at 100 kHz, low leakage current density of 2.0 × 10^?7 A/cm² at 0.1 MV/cm, and high P_r and d₃₃ values of 15.4 μC/cm² and 124 pm/V at 100 kV/cm, respectively.     

Effect of SrTiO3 content on the growth of (100−x)(K0.5Na0.5)NbO3–xSrTiO3 lead-free piezoelectric single crystals grown by the solid-state crystal growth method

In the present work, the single crystal growth by solid-state crystal growth of (100?x)(K_0.5Na_0.5)NbO₃–xSrTiO₃, where x?=?0,1,2,3?mol-%, has been examined in order to study the effect of SrTiO₃ content on single crystal growth. Powders were prepared by the conventional mixed oxide method. <001> KTaO₃ seed crystals were buried in the powders, pressed into pellets and sintered at 1100°C for 1, 3, 5 and 10?h. Single crystals of the ceramic compositions grew onto the seeds. For the (K_0.5Na_0.5)NbO₃ sample, both single crystal growth and abnormal grain growth in the matrix began to take place within 1?h. As the amount of SrTiO₃ increased, the onset of both single crystal growth and abnormal grain growth were delayed. The effect of SrTiO₃ addition on the single crystal and matrix grain growth behaviour is explained in terms of the mixed control theory of grain growth.     

Dielectric and piezoelectric properties of lead-free (K0.44Na0.46)NbO3-0.5%MnO2 single crystals grown by the TSSG method

Lead-free (K_0.44Na_0.46)NbO₃-0.5%MnO₂ (KNN-0.5%MnO₂) single crystals with dimensions of Ф30×10 mm were successfully grown by a top seeded solution growth technique (TSSG). The X-ray diffraction pattern has shown that the as-grown crystals have an orthorhombic perovskite structure. The orthorhombic-tetragonal (T_O-T) and tetragonal-cubic phase transition temperature (the Curie temperature T_C) of the single crystal were found at 184 °C and 412 °C, respectively. The KNN-0.5%MnO₂ single crystals exhibited high piezoelectric constants d₃₃ and dielectric permittivity ε_r, being 261 pC/N and 275. Well saturated P-E hysteresis loop with remnant polarization P_r=22.06 µC/cm² and coercive field E_c=17.93 kV/cm was obtained at a maximum electric field of 3 kV/mm. A high strain (0.24%) and electromechanical coupling coefficient K_t (65.9%) were obtained along the (001) orientation. These excellent results indicated that the KNN-0.5%MnO₂ single crystals could be used as high quality lead-free material.     

Seed‐Free Solid‐State Growth of Large Lead‐Free Piezoelectric Single Crystals: (Na1/2K1/2)NbO3

Large Na_0.5K_0.5NbO₃ (NKN) piezoelectric single crystals were obtained by seed‐free solid‐state crystal growth method, which is a traditional sintering grain growth process, with LiBiO₃ used as a sintering aid. The largest dimension of the single crystals obtained was 11 mm × 9 mm × 3 mm. In addition to the LiBiO₃ doping content, temperature, and time effect of the crystal growth process was systematically investigated and considered from the kinetics point of view. With the assistance of Avrami analysis, parameters relevant to the crystal growth process were determined. Laue diffraction and transmission electron microscopy suggested an orthorhombic symmetry for the single crystalline structure. Dielectric‐frequency‐temperature measurements revealed an orthorhombic‐tetragonal and tetragonal‐cubic phase transition at 155°C and 405°C, respectively, both of which are typical of first‐order transitions, and have a well‐defined thermal hysteresis. Rayleigh analysis was performed regarding to the extrinsic reversible and nonreversible piezoelectric properties, and the result suggested a dominant intrinsic reversible piezoelectric contribution of 91.5% under E₀ = 1 kV/cm AC amplitude. Such a single crystal growth process route is low cost and a relative simple preparation process.     

Preparation and characterization of (K0.5Na0.5)NbO3 ceramics

In this paper the preparation and characterization of the ceramic material (K_0.5Na_0.5)NbO₃ (KNN) has been studied. Although conventional processing of KNN is often reported to result in sintered bodies lacking sufficient density, samples produced in this work exhibit theoretical density over 95% and yield superior piezoelectric properties than those obtained by the same method and reported previously. The electromechanical coupling coefficient in the thickness direction, k_t, is found to reach 45%. Apart from k_t, the piezoelectric coefficients in longitudinal and planar directions (d₃₃ of 100pC/N and d₃₁ of 43pC/N), hysteresis loop, pyroelectric coefficient measurements and dielectric properties are presented.     

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.     

Microstructural changes in (K0.5Na0.5)NbO3 ceramics sintered in various atmospheres

(K_0.5Na_0.5)NbO₃ is a potential lead-free piezoelectric ceramic, but often suffers from abnormal grain growth. Previous work on BaTiO₃ and SrTiO₃ has shown that abnormal grain growth can be suppressed by controlling the sintering atmosphere. In the present work, (K_0.5Na_0.5)NbO₃ was sintered in atmospheres ranging from O₂ to H₂ and the effect on grain growth behaviour studied. Sintering in reducing atmospheres causes a delay in the onset and a reduction in the amount of abnormal grain growth. The effect of sintering atmosphere on grain growth behaviour can be explained using the 2D nucleation-controlled theory of grain growth. Changes in the grain shape during sintering in reducing atmospheres indicate a reduction in the edge free energy of (K_0.5Na_0.5)NbO₃ caused by an increase in the concentration of oxygen vacancies. This decreases the critical driving force necessary for rapid grain growth and causes a transition from abnormal to pseudo-normal followed by abnormal grain growth.     

Structural,magnetic and electrical properties of K0.5Na0.5NbO3 doped NiZnCo ferrite for high frequency device

Ni_0.6Zn_0.4Co_0.2Fe_1.8O₄ ferrites doped with x wt.% K_0.5Na_0.5NbO₃ (0.00≤x≤1.00) were successfully prepared by solid-state reaction method. The lattice parameters a decreased and the diffraction peak of (311) shifted to higher angle with the increase of K_0.5Na_0.5NbO₃ (KNN) content. The grain size D initially increased to 3.12 μm (x = 0.50) and then reduced to 2.66 μm (x=1.00). The study also showed the addition of KNN effectively improved magnetic and electrical properties of NiZnCo ferrites. The saturation magnetization Ms decreased from 60.59 to 46.11 emu/g and the coercivity Hc overall showed a decreasing trend from 84.64–67.00 Oe. The dielectric constant ε´ of prepared samples increased when x≤0.75, then decreased when x>0.75, and all prepared samples had low loss tangent tanδ at high frequency. In addition, all samples exhibited high resistivity ρ and activation energy E_ρ.     

Compositional range and electrical properties of the morphotropic phase boundary in the Na0.5Bi0.5TiO3–K0.5Bi0.5TiO3 system

We have investigated the Na_0.5Bi_0.5TiO₃–K_0.5Bi_0.5TiO₃ (NBT–KBT) system, with its complex perovskite structure, as a promising material for piezoelectric applications. The NBT–KBT samples were synthesized using a solid-state reaction method and characterized with XRD and SEM. Room-temperature XRD showed a gradual change in the crystal structure from tetragonal in the KBT to rhombohedral in the NBT, with the presence of an intermediate morphotropic region in the samples with a compositional fraction x between 0.17 and 0.25. The fitted perovskite lattice parameters confirmed an increase in the size of the crystal lattice from NBT towards KBT, which coincides with an increase in the ionic radii. Electrical measurements on the samples showed that the maximum values of the dielectric constant, the remanent polarization and the piezoelectric coefficient are reached at the morphotropic phase boundary (MPB) (? = 1140 at 1 MHz; P_r = 40 μC/cm²; d₃₃ = 134 pC/N).