High‐Performance [001]c‐Textured PNN‐PZT Relaxor Ferroelectric Ceramics for Electromechanical Coupling Devices

[001]_C‐Textured 0.55Pb(Ni_1/3Nb_2/3)O₃–0.15PbZrO₃–0.3PbTiO₃ (PNN‐PZT) ceramics are prepared by the templated grain‐growth method using BaTiO₃ (BT) platelet templates. Samples with different template contents are fabricated and compared in terms of texture fraction, microstructure, and piezoelectric, ferroelectric and dielectric properties. High piezoelectric performance (d₃₃ = 1210 pC N^?1, d₃₃* = 1773 pm V^?1 at 5 kV cm^?1) and high figure of merit g₃₃?d₃₃ (21.92 × 10^?12 m² N^?1) are achieved in the [001]_C‐textured PNN‐PZT ceramic with 2 vol% BaTiO₃ template, for which the texture fraction is 82%. In addition, domain structures of textured PNN‐PZT ceramics are observed and analyzed, which provide clues to the origin of the giant piezoelectric and electromechanical coupling properties of PNN‐PZT ceramics.     

Grain Boundary Diffusion Hardening in Potassium Sodium Niobate-Based Ceramics with Full Gradient Composition and High Piezoelectricity

Reducing mechanical losses and suppressing self-heating are critical characteristics for high-power piezoelectric applications. For environmentally friendly Pb-free piezoelectric ceramics, traditional acceptor doping or annealing treatments have successfully improved the mechanical quality factor (Q_m) based on a ceramic matrix with a poor piezoelectric coefficient (d₃₃<100 pC/N). Nevertheless, a ceramic with high Q_m and d₃₃ values has not been reported owing to the inverse relationship between Q_m and d₃₃. Herein, a novel hardening method called grain boundary diffusion is used to develop Pb-free potassium sodium niobate ceramics, where Q_m increased by more than two-fold (from 51 to 132) and a high d₃₃ value (d₃₃ = 360 pC/N) is maintained. Significantly, d₃₃ retained 98% of its initial value after 180 days, exhibiting improved aging stability. The established properties are associated with the formation of the core-shell microstructure and the full gradient composition distribution using structural characterizations and phase-field simulations, where the core maintains a high d₃₃ and the shell provides a hardening effect. The novel hardening effect in piezoelectric materials, known as grain boundary diffusion hardening, highlights the enhancement of the mechanical quality factor with high piezoelectricity, providing a new paradigm for the design of functional materials.     

Temperature‐Insensitive (K,Na)NbO3‐Based Lead‐Free Piezoactuator Ceramics

The development of lead‐free piezoceramics has attracted great interest because of growing environmental concerns. A polymorphic phase transition (PPT) has been utilized in the past to tailor piezoelectric properties in lead‐free (K,Na)NbO₃ (KNN)‐based materials accepting the drawback of large temperature sensitivity. Here a material concept is reported, which yields an average piezoelectric coefficientd₃₃ of about 300 pC/N and a high level of unipolar strain up to 0.16% at room temperature. Most intriguingly, field‐induced strain varies less than 10% from room temperature to 175 °C. The temperature insensitivity of field‐induced strain is rationalized using an electrostrictive coupling to polarization amplitude while the temperature‐dependent piezoelectric coefficient is discussed using localized piezoresponse probed by piezoforce microscopy. This discovery opens a new development window for temperature‐insensitive piezoelectric actuators despite the presence of a polymorphic phase transition around room temperature.     

Giant Piezoelectricity of Ternary Perovskite Ceramics at High Temperatures

Here, novel ferroelectric ceramics of (0.95 ? x)BiScO₃‐xPbTiO₃‐0.05Pb(Sn_1/3Nb_2/3)O₃ (BS‐xPT‐PSN) of complex perovskite structure are reported with compositions near the morphotropic phase boundary (MPB), and which exhibit a piezoelectric coefficient d₃₃ = 555 pC N^?1, a large‐signal coefficient $d_{33}^{?}$ ≈ 1200 pm V^?1 at room temperature, and a high Curie temperature T_C of 408 °C. More interestingly, this ternary system exhibits a giant and stable piezoelectric response at 200 °C with a large‐signal $d_{33}^{?}$ ≈ 2500 pm V^?1, matching that of the costly relaxor‐based piezoelectric single crystals at room temperature. The mechanisms of such giant piezoelectricity and its characteristic temperature dependence are attributed to the spontaneous polarization rotation and extension under an electric field and the MPB‐related phase transition. The findings reveal that the BS‐xPT‐PSN ceramics constitute a new family of high‐performance piezoelectric materials suitable for electromechanical transducers that can be operated at high temperatures (at 200 °C, or higher).     

Flexible Piezoelectric Touch Sensor by Alignment of Lead‐Free Alkaline Niobate Microcubes in PDMS

A highly sensitive, lead‐free, and flexible piezoelectric touch sensor is reported based on composite films of alkaline niobate K_0.485Na_0.485Li_0.03NbO₃ (KNLN) powders aligned in a polydimethylsiloxane (PDMS) matrix. KNLN powder is fabricated by solid‐state sintering and consists of microcubes. The particles are dispersed in uncured PDMS and oriented by application of an oscillating dielectrophoretic alignment field. The dielectric constant of the composite film is almost independent of the microstructure, while upon alignment the piezoelectric charge coefficient increases more than tenfold up to 17 pC N^?1. A quantitative analysis shows that the origin is a reduction of the interparticle distance to under 1.0 µm in the aligned bicontinuous KNLN chains. The temperature stable piezoelectric voltage coefficient exhibits a maximum value of 220 mV m N^?1, at a volume fraction of only 10%. This state‐of‐the‐art value outperforms bulk piezoelectric ceramics and composites with randomly dispersed particles, and is comparable to the values reported for the piezoelectric polymers polyvinylidenefluoride and its random copolymer with trifluoroethylene. Optimized composite films are incorporated in flexible piezoelectric touch sensors. The high sensitivity is analyzed and discussed. As the fabrication technology is straightforward and easy to implement, applications are foreseen in flexible electronics such as wireless sensor networks and biodiagnostics.     

Giant Piezoelectric Coefficients in Relaxor Piezoelectric Ceramic PNN‐PZT for Vibration Energy Harvesting

It is well known that the piezoelectric performance of ferroelectric Pb(Zr,Ti)O₃ (PZT) based ceramics is far inferior to that of ferroelectric single crystals due to ceramics' polycrystalline nature. Herein, it is reported that piezoelectric stress coefficient e₃₃ = 39.24 C m^?2 (induced electric displacement under applied strain) in the relaxor piezoelectric ceramic 0.55Pb(Ni_1/3Nb_2/3)O₃–0.135PbZrO₃–0.315PbTiO₃ (PNN‐PZT) prepared by the solid state reaction method exhibits the highest value among various reported ferroelectric ceramic and single crystal materials. In addition, its piezoelectric coefficient d₃₃* = 1753 pm V^?1 is also comparable with that of the commercial Pb(Mg_1/3Nb_2/3)O₃‐PbTiO₃ (PMN‐PT) piezoelectric single crystal. The PNN‐PZT ceramic is then assembled into a cymbal energy harvester. Notably, its maximum output current at the acceleration of 3.5 g is 2.5 mA_pp, which is four times of the PMN‐PT single crystal due to the large piezoelectric e₃₃ constants; while the maximum output power is 14.0 mW, which is almost the same as the PMN‐PT single crystal harvester. The theoretical analysis on force‐induced power output is also presented, which indicates PNN‐PZT ceramic has great potential for energy device application.     

Multifunctional Artificial Artery from Direct 3D Printing with Built‐In Ferroelectricity and Tissue‐Matching Modulus for Real‐Time Sensing and Occlusion Monitoring

Treating vascular grafts failure requires complex surgery procedures and is associated with high risks. A real‐time monitoring vascular system enables quick and reliable identification of complications and initiates safer treatments early. Here, an electric fieldassisted 3D printing technology is developed to fabricate in situ‐poled ferroelectric artificial arteries that offer battery‐free real‐time blood pressure sensing and occlusion monitoring capability. The functional artery architecture is made possible by the development of a ferroelectric biocomposite which can be quickly polarized during printing and reshaped into devised objects. The synergistic effect from the potassium sodium niobite particles and the polyvinylidene fluoride polymer matrix yields a superb piezoelectric performance (bulk‐scale d₃₃ > 12 pC N^?1). The sinusoidal architecture brings the mechanical modulus close to the level of blood vessels. The desired piezoelectric and mechanical properties of the artificial artery provide an excellent sensitivity to pressure change (0.306 mV mmHg^?1, R² > 0.99) within the range of human blood pressure (11.25–225.00 mmHg). The high pressure sensitivity and the ability to detect subtle vessel motion pattern change enable early detection of partial occlusion (e.g., thrombosis), allowing for preventing grafts failure. This work demonstrates a promising strategy of incorporating multifunctionality to artificial biological systems for smart healthcare systems.     

A New Material for High‐Temperature Lead‐Free Actuators

Unimorph cantilevers are made from 0.5BaTiO₃‐0.5Sm₂O₃ (BTO‐SmO) self‐assembled vertical heteroepitaxial nanocomposite thin films, grown by PLD on (001) SrTiO₃ single crystal substrates. The films remain piezoelectric up to at least 250 °C without losing any actuation. The longitudinal piezoelectric coefficient, d₃₃, is ≈45 to 50 pm V^?1 measured from room temperature to 250 °C. The transverse piezoelectric coefficient, d₃₁, a key parameter of actuator performance, exceeds PZT (Pb_1–xZr_xTiO₃) films at >200 pm V^?1. Since the d₃₁ coefficient was found to be positive, this opens up exciting new applications opportunities. The possible reasons for d₃₁ > 0 are discussed in the light of 3D strain control in the nanocomposites.     

Enhancing Piezoelectric Performance of CaBi2Nb2O9 Ceramics Through Microstructure Control

Calcium bismuth niobate (CaBi₂Nb₂O₉, CBN) is a high-Curie-temperature (T _C) piezoelectric material with relatively poor piezoelectric performance. Attempts were made to enhance the piezoelectric and direct-current (DC) resistive properties of CBN ceramics by increasing their density and controlling their microstructural texture, which were achieved by combining the templated grain growth and hot pressing methods. The modified CBN ceramics with 97.5% relative density and 90.5% Lotgering factor had much higher piezoelectric constant (d ₃₃ = 20 pC/N) than those prepared by the normal sintering process (d ₃₃ = 6 pC/N). High-temperature alternating-current (AC) impedance spectroscopy of the CBN ceramics was measured by using an impedance/gain-phase analyzer. Their electrical resistivity was approximately 6.5 × 10⁴ Ω cm at 600°C. Therefore, CBN ceramics can be used for high-temperature piezoelectric applications.     

Unidirectional High‐Power Generation via Stress‐Induced Dipole Alignment from ZnSnO3 Nanocubes/Polymer Hybrid Piezoelectric Nanogenerator

The extremely stable high‐power generation from hybrid piezoelectric nanogenerator (HP‐NG) based on a composite of single‐crystalline piezoelectric perovskite zinc stannate (ZnSnO₃) nanocubes and polydimethylsiloxane without any electrical poling treatment is reported. The HP‐NG generates large power output under only vertical compression, while there is negligible power generation with other configurations of applied strain, such as bending and folding. This unique high unidirectionality of power generation behavior of the HP‐NG provides desirable features for large‐area piezoelectric power generation based on vertical mechanical compression such as moving vehicles, railway transport, and human walking. The HP‐NGs of ZnSnO₃ nanocubes exhibit high mechanical durability, excellent robustness, and high power‐generation performance. A large recordable output voltage of about 20 V and an output current density value of about 1 μA cm^?2 are successfully achived, using a single cell of HP‐NG obtained under rolling of a vehicle tire.     

Structural Stabilization and Piezoelectric Enhancement in Epitaxial (Ti1−xMgx)0.25Al0.75N(0001) Layers

Epitaxial (Ti_1?xMg_x)_0.25Al_0.75N(0001)/Al₂O₃(0001) layers are used as a model system to explore how Fermi‐level engineering facilitates structural stabilization of a host matrix despite the intentional introduction of local bonding instabilities that enhance the piezoelectric response. The destabilizing octahedral bonding preference of Ti dopants and the preferred 0.67 nitrogen‐to‐Mg ratio for Mg dopants deteriorate the wurtzite AlN matrix for both Ti‐rich (x < 0.2) and Mg‐rich (x ≥ 0.9) alloys. Conversely, x = 0.5 leads to a stability peak with a minimum in the lattice constant ratio c/a, which is caused by a Fermi‐level shift into the bandgap and a trend toward nondirectional ionic bonding, leading to a maximum in the expected piezoelectric stress constant e₃₃. The refractive index and the subgap absorption decrease with x, the optical bandgap increases, and the elastic constant along the hexagonal axis C₃₃ = 270 ± 14 GPa remains composition independent, leading to an expected piezoelectric constant d₃₃ = 6.4 pC N^?1 at x = 0.5, which is 50% larger than for the pure AlN matrix. Thus, contrary to the typical anticorrelation between stability and electromechanical coupling, the (Ti_1?xMg_x)_0.25Al_0.75N system exhibits simultaneous maxima in the structural stability and the piezoelectric response at x = 0.5.     

Diffused Phase Transition Boosts Thermal Stability of High‐Performance Lead‐Free Piezoelectrics

High piezoelectricity of (K,Na)NbO₃ (KNN) lead‐free materials benefits from a polymorphic phase transition (PPT) around room temperature, but its temperature sensitivity has been a bottleneck impeding their applications. It is found that good thermal stability can be achieved in CaZrO₃‐modified KNN lead‐free piezoceramics, in which the normalized strain d ₃₃* almost keeps constant from room temperature up to 140 °C. In situ synchrotron X‐ray diffraction experiments combined with permitivity measurements disclose the occurrence of a new phase transformation under an electrical field, which extends the transition range between tetragonal and orthorhombic phases. It is revealed that such an electrically enhanced diffused PPT contributed to the boosted thermal stability of KNN‐based lead‐free piezoceramics with high piezoelectricity. The present approach based on phase engineering should also be effective in endowing other lead‐free piezoelectrics with high piezoelectricity and good temperature stability.     

A New Phase Boundary in (Bi1/2Na1/2)TiO3−BaTiO3 Revealed via a Novel Method of Electron Diffraction Analysis

A new phase boundary is revealed in (1–x)(Bi_1/2Na_1/2)TiO₃?xBaTiO₃, the most extensively studied lead‐free piezoelectric solid solution. This discovery results from a novel method of electron diffraction analysis, which allows the precise determination of oxygen octahedra tilting in multi‐domain perovskite ferroelectrics. The study using this method supports the recently proposed Cc symmetry for pure (Bi_1/2Na_1/2)TiO₃, and, more importantly, indicates the crystal structure evolves into the R3c symmetry with the addition of BaTiO₃, forming a Cc/R3c phase boundary at x = 3–4%. In the poling field E_pol versus composition x phase diagram for polycrystalline ceramics, this phase boundary exists with E_pol below 5.5 kV mm^?1; the Cc phase is transformed to the R3c phase during poling at higher fields. The results reported here provide the microstructural origin for the previously unexplained strain behavior and clarify the low‐BaTiO₃‐content phase relationship in this popular lead‐free piezoelectric system.     

Microstructure,Phase Transition,and Electrical Properties of K<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Na<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>NbO<Subscript>3</Subscript> Lead-Free Piezoceramics

The microstructure, phase transition, and electrical properties of lead-free K _x Na_1−x NbO₃ (x = 0.46 to 0.51, abbreviated as KNN) piezoceramics prepared by a conventional solid-state reaction method were investigated with an emphasis on the influence of the K/Na ratio. Scanning electron microscopy (SEM) images showed that the grain growth was slightly improved by increasing x. However, all ceramic samples possessed high densifications with fine grains from several hundred nanometers to several micrometers. X-ray diffraction (XRD) results showed that a discontinuous change of lattice parameters appeared between x = 0.49 and 0.50, which suggested a typical morphotropic phase boundary (MPB) separating two different orthorhombic phases O _I and O _II. The sample with composition x = 0.49 had the peak values of the piezoelectric constant d ₃₃ of 146 pC/N and the planar electromechanical coupling coefficient k _p of 43%. These results indicated that improving the piezoelectric properties in KNN ceramics could be achieved by optimizing the K/Na ratio.     

Poled Sol–Gel Materials With Heterocycle Push–Pull Chromophores that Confer Enhanced Second‐Order Optical Nonlinearity

Hybrid organic–inorganic materials doped with zwitterionic push–pull chromophores with high hyperpolarizability have been synthesized by a sol–gel procedure. A large chromophore concentration was reached by using N‐(hydroxyethyl)carbazole as a physical spacer (preventing the dye aggregation). Spin‐coated doped films were electrically poled and second harmonic generation measurements performed in situ. During the thermally assisted poling under a N₂ atmosphere, only the carbazole molecules degraded. Second‐harmonic generation measurements gave an estimation of the nonlinear coefficient, r₃₃, of 38 pm V^–1 at 1064 nm.     

Solution‐Processed Small‐Molecule Bulk Heterojunction Ambipolar Transistors

Solution‐processed small‐molecule bulk heterojunction (BHJ) ambipolar organic thin‐film transistors are fabricated based on a combination of [2‐phenylbenzo[d,d']thieno[3,2‐b;4,5‐b']dithiophene (P‐BTDT) : 2‐(4‐n‐octylphenyl)benzo[d,d ']thieno[3,2‐b;4,5‐b']dithiophene (OP‐BTDT)] and C₆₀. Treating high electrical performance vacuum‐deposited P‐BTDT organic semiconductors with a newly developed solution‐processed organic semiconductor material, OP‐BTDT, in an optimized ratio yields a solution‐processed p‐channel organic semiconductor blend with carrier mobility as high as 0.65 cm² V^?1 s^?1. An optimized blending of P‐BTDT:OP‐BTDT with the n‐channel semiconductor, C₆₀, results in a BHJ ambipolar transistor with balanced carrier mobilities for holes and electrons of 0.03 and 0.02 cm² V^?1 s^?1, respectively. Furthermore, a complementary‐like inverter composed of two ambipolar thin‐film transistors is demonstrated, which achieves a gain of 115.     

Solid‐Phase Synthesis of Molecularly Imprinted Polymer Nanoparticles with a Reusable Template–“Plastic Antibodies”

Molecularly imprinted polymers (MIPs) are generic alternatives to antibodies in sensors, diagnostics, and separations. To displace biomolecules without radical changes in infrastructure in device manufacture, MIPs should share their characteristics (solubility, size, specificity and affinity, localized binding domain) whilst maintaining the advantages of MIPs (low‐cost, short development time, and high stability) hence the interest in MIP nanoparticles. Herein, a reusable solid‐phase template approach is reported (fully compatible with automation) for the synthesis of MIP nanoparticles and their precise manufacture using a prototype automated UV photochemical reactor. Batches of nanoparticles (30–400 nm) with narrow size distributions imprinted with: melamine (d = 60 nm, K_d = 6.3 × 10^?8 M ), vancomycin (d = 250 nm, K_d = 3.4 × 10^?9 M ), a peptide (d = 350 nm, K_d = 4.8 × 10^?8 M ) and proteins have been produced. The instrument uses a column packed with glass beads, bearing the template. Process parameters are under computer control, requiring minimal manual intervention. For the first time, the reliable re‐use of molecular templates is demonstrated in the synthesis of MIPs (≥30 batches of nanoMIPs without loss of performance). NanoMIPs are produced template‐free and the solid‐phase acts both as template and affinity separation medium.     

Effect of the Addition of B2O3 on the Density, Microstructure, Dielectric, Piezoelectric and Ferroelectric Properties of K0.5Na0.5NbO3 Ceramics

Boron oxide (B₂O₃) addition to pre-reacted K_0.5Na_0.5NbO₃ (KNN) powders facilitated swift densification at relatively low sintering temperatures which was believed to be a key to minimize potassium and sodium loss. The base KNN powder was synthesized via solid-state reaction route. The different amounts (0.1–1 wt%) of B₂O₃ were-added, and ceramics were sintered at different temperatures and durations to optimize the amount of B₂O₃ needed to obtain KNN pellets with highest possible density and grain size. The 0.1 wt% B₂O₃-added KNN ceramics sintered at 1,100 °C for 1 h exhibited higher density (97 %). Scanning electron microscopy studies confirmed an increase in average grain size with increasing B₂O₃ content at appropriate temperature of sintering and duration. The B₂O₃-added KNN ceramics exhibited improved dielectric and piezoelectric properties at room temperature. For instance, 0.1 wt% B₂O₃-added KNN ceramic exhibited d ₃₃ value of 116 pC/N which is much higher than that of pure KNN ceramics. Interestingly, all the B₂O₃-added (0.1–1 wt%) KNN ceramics exhibited polarization–electric field (P vs. E) hysteresis loops at room temperature. The remnant polarization (P _r) and coercive field (E _c) values are dependent on the B₂O₃ content and crystallite size.     

Complete Set of Material Constants of ?011?-Poled Rhombohedral Single-Crystal 0.25Pb(In1/2Nb1/2)O3-0.47Pb(Mg1/3Nb2/3)O3-0.28PbTiO3

The complete set of elastic, dielectric, and piezoelectric constants of a 0.25Pb(In_1/2Nb_1/2)O₃-0.47Pb(Mg_1/3Nb_2/3)O₃-0.28PbTiO₃ ternary relaxor ferroelectric single crystal after 〈011〉 poling was determined by ultrasonic and resonance methods. It exhibited a rhombohedral structure as determined by powder x-ray diffraction (XRD) and x-ray fluorescence (XRF) analysis. The electromechanical coupling factor k ₁₅ and piezoelectric coefficient d ₁₅ for shear mode are 0.93 pC/N and 2658 pC/N, and k ₃₂ and d ₃₂ for transverse mode are 0.91 pC/N and -1337 pC/N, respectively. More importantly, the rhombohedral to orthorhombic phase-transition temperature is much higher than that of PZN-0.07PT or PMN-0.29PT.     

Ultrahigh Energy‐Storage Density in NaNbO3‐Based Lead‐Free Relaxor Antiferroelectric Ceramics with Nanoscale Domains

Dielectric energy‐storage capacitors have received increasing attention in recent years due to the advantages of high voltage, high power density, and fast charge/discharge rates. Here, a new environment‐friendly 0.76NaNbO₃–0.24(Bi_0.5Na_0.5)TiO₃ relaxor antiferroelectric (AFE) bulk ceramic is studied, where local orthorhombic Pnma symmetry (R phase) and nanodomains are observed based on high‐resolution transmission electron microscopy, selected area electron diffraction, and in/ex situ synchrotron X‐ray diffraction. The orthorhombic AFE R phase and relaxor characteristics synergistically contribute to the record‐high energy‐storage density W_rec of ≈12.2 J cm^?3 and acceptable energy efficiency η ≈ 69% at 68 kV mm^?1, showing great advantages over currently reported bulk dielectric ceramics. In comparison with normal AFEs, the existence of large random fields in the relaxor AFE matrix and intrinsically high breakdown strength of NaNbO₃‐based compositions are thought to be responsible for the observed energy‐storage performances. Together with the good thermal stability of W_rec (>7.4 J cm^?3) and η (>73%) values at 45 kV mm^?1 up to temperature of 200 °C, it is demonstrated that NaNbO₃‐based relaxor AFE ceramics will be potential lead‐free dielectric materials for next‐generation pulsed power capacitor applications.