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.     

Simulation and calculation of the piezoelectric modulus of a lead zirconate-titanate thin film in a test microstructure

Results of simulation of stresses in the test structure of a silicon beam and analytical calculation of piezoelectric modulus d ₃₁ of a lead zirconate-titanate (PZT) thin film arranged in the region of an elastic element are presented. The characteristics of the sensitive element of acceleration are calculated based on a PZT thin film with an inertial mass made of silicon.     

Sustainable Vibration Energy Harvesting Based on Zr‐Doped PMN‐PT Piezoelectric Single Crystal Cantilevers

In this paper, we present the results of a preliminary study on the piezoelectric energy harvesting performance of a Zr‐doped PbMg_1/3Nb_2/3O₃‐PbTiO₃ (PMN‐PZT) single crystal beam. A novel piezoelectric beam cantilever structure is used to demonstrate the feasibility of generating AC voltage during a state of vibration. The energy‐harvesting capability of a PMN‐PZT beam is calculated and tested. The frequency response of the cantilever device shows that the first mode resonance frequency of the excitation model exists in the neighborhood of several hundreds of hertz, which is similar to the calculated value. These tests show that several significantly open AC voltages and sub‐mW power are achieved. To test the possibility of a small scale power source for a ubiquitous sensor network service, energy conversion and the testing of storage experiment are also carried out.     

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.     

In Vivo Self‐Powered Wireless Transmission Using Biocompatible Flexible Energy Harvesters

Additional surgeries for implantable biomedical devices are inevitable to replace discharged batteries, but repeated surgeries can be a risk to patients, causing bleeding, inflammation, and infection. Therefore, developing self‐powered implantable devices is essential to reduce the patient's physical/psychological pain and financial burden. Although wireless communication plays a critical role in implantable biomedical devices that contain the function of data transmitting, it has never been integrated with in vivo piezoelectric self‐powered system due to its high‐level power consumption (microwatt‐scale). Here, wireless communication, which is essential for a ubiquitous healthcare system, is successfully driven with in vivo energy harvesting enabled by high‐performance single‐crystalline (1 ? x )Pb(Mg_1/3Nb_2/3)O₃?(x )Pb(Zr,Ti)O₃ (PMN‐PZT). The PMN‐PZT energy harvester generates an open‐circuit voltage of 17.8 V and a short‐circuit current of 1.74 µA from porcine heartbeats, which are greater by a factor of 4.45 and 17.5 than those of previously reported in vivo piezoelectric energy harvesting. The energy harvester exhibits excellent biocompatibility, which implies the possibility for applying the device to biomedical applications.     

High Performance Piezoelectric Microspeakers and Thin Speaker Array System

This paper reports on an improved piezoelectric microspeaker with a high sound pressure level of 90 dB, a total harmonic distortion of less than 15%, and coherence higher than 0.9. The fabricated Pb(Zr,Ti)O₃ (PZT) microspeakers have a thickness of only 1 mm including the speaker frame and an active area of 18 mm×20 mm. To achieve higher sound pressure and lower distortion, the PZT piezoelectric microspeaker has a well‐designed speaker frame and a piezoelectric diaphragm consisting of a tilted PZT membrane and silicone buffer layer. From the simulation and measurement results, we confirmed that the silicon buffer layer can lower the first resonant frequency, which enhances the microspeaker's sound pressure at a low frequency range and can also reduce useless distortion generated by the harmonics. The fabricated PZT piezoelectric microspeakers are implemented on a multichannel speaker array system for personal acoustical space generation. The output sound pressure at a 30 cm distance away from the center of the speaker line array is 15 dB higher than the sound pressure at the neighboring region 30 degrees from the vertical axis.     

Low Fatigue in Epitaxial Pb(Zr<Subscript>0.2</Subscript>Ti<Subscript>0.8</Subscript>)O<Subscript>3</Subscript> on Si Substrates with LaNiO<Subscript>3</Subscript> Electrodes by RF Sputtering

Epitaxial PZT (001) thin films with a LaNiO₃ bottom electrode were deposited by radio-frequency (RF) sputtering onto Si(001) single-crystal substrates with SrTiO₃/TiN buffer layers. Pb(Zr_0.2Ti_0.8)O₃ (PZT) samples were shown to consist of a single perovskite phase and to have an (001) orientation. The orientation relationship was determined to be PZT(001)[110]∥LaNiO₃(001)[110]∥SrTiO₃ (001)[110]∥TiN(001)[110]∥Si(001)[110]. Atomic force microscope (AFM) measurements showed the PZT films to have smooth surfaces with a roughness of 1.15 nm. The microstructure of the multilayer was studied using transmission electron microscopy (TEM). Electrical measurements were conducted using both Pt and LaNiO₃ as top electrodes. The measured remanent polarization P _r and coercive field E _c of the PZT thin film with Pt top electrodes were 23 μC/cm² and 75 kV/cm, and were 25 μC/cm² and 60 kV/cm for the PZT film with LaNiO₃ top electrodes. No obvious fatigue after 10¹⁰ switching cycles indicated good electrical endurance of the PZT films using LaNiO₃ electrodes, compared with the PZT film with Pt top electrodes showing a significant polarization loss after 10⁸ cycles. These PZT films with LaNiO₃ electrodes could be potential recording media for probe-based high-density data storage.     

Nanocrystalline Electroplated Cu–Ni: Metallic Thin Films with Enhanced Mechanical Properties and Tunable Magnetic Behavior

Nanocrystalline 3 µm thick Cu_1–xNi_x (0.45 ≤ x ≤ 0.87) films are electrodeposited galvanostatically onto Cu/Ti/Si (100) substrates, from a citrate‐ and sulphate‐based bath containing sodium lauryl sulphate and saccharine as additives. The films exhibit large values of reduced Young's modulus (173 < E_r < 192 GPa) and hardness (6.4 < H < 8.2 GPa), both of which can be tailored by varying the alloy composition. The outstanding mechanical properties of these metallic films can be ascribed to their nanocrystalline nature—as evidenced by X‐ray diffraction, transmission electron microscopy, and atomic force microscopy—along with the occurrence of stacking faults and the concomitant formation of intragranular nanotwins during film growth. Due to their nanocrystalline character, these films also show very low surface roughness (root mean square deviation of around 2 nm). Furthermore, tunable magnetic properties, including a transition from paramagnetic to ferromagnetic behavior, are observed when the Ni percentage is increased. This combination of properties, together with the simplicity of the fabrication method, makes this system attractive for widespread technological applications, including hard metallic coatings or magnetic micro/nano‐electromechanical devices.     

Mobile Ferroelastic Domain Walls in Nanocrystalline PZT Films: the Direct Piezoelectric Effect

Ferroelastic (90°) domain wall motion occurs readily in bulk samples of displacive ferroelectrics such as Pb(Zr,Ti)O₃ (PZT), dictating critical piezoelectric, dielectric, and polarization switching properties. Many prior studies have used converse piezoelectric measurements to probe the dynamics of ferroelastic domains in thin films; however, such experiments are strongly influenced by the mechanical clamping effect of the substrate, which inhibits electric field‐induced 90° domain wall motion. Nevertheless, these observations raise a tantalizing question: Does the application of mechanical stress, rather than electric field, result in an entirely different response in thin films? Here we report biaxial stress‐driven crystallographic reorientation of (100)/(001) textured, 70 nm thick Pb(Zr_0.25Ti_0.75)O₃ films via 90° domain wall motion, measured in situ by both x‐ray diffraction and piezoforce microscopy. Visual evidence of nanoscale mechanisms that underlie the direct piezoelectric effect is shown. Mobile 90° domain walls effect complete orientation switching in the grains in which they operate, without apparent wall pinning, indicating that bulk‐like ferroelastic behavior can extend to nanocrystalline films in the absence of substrate clamping.     

Optimization of Pb(Zr0.53,Ti0.47)O3 films for micropower generation using integrated cantilevers

Lead zirconate titanate, Pb(Zr_0.53,Ti_0.47)O₃ or PZT, thin films and integrated cantilevers have been fabricated for energy harvesting applications. The PZT films were deposited on PECVD SiO₂/Si substrates with a sol-gel derived ZrO₂ buffer layer. It is found that lead content in the starting solution and ramp rate during film crystallization are critical to achieving large-grained films on the ZrO₂ surface. The electrical properties of the PZT films were measured using metal-ferroelectric-metal and inter-digital electrode structures, and revealed substantial improvement in film properties by controlling the process conditions. Functional cantilevers are demonstrated using the optimized films with output of 1.4 V peak-to-peak at 1 kHz and 2.5 g.     

压电薄膜自适应变形微反射镜阵列研究

介绍了自适应光学系统中的一种全新的基于Pb（ZrxTi1-xO3）（PZT）薄膜的微反射镜阵列。通过控制PZT薄膜两端电压实现微镜单元的微量形变，改变反射镜局部面形，校正畸变波面的波差，改善成像质量。该方案在重掺杂Si片基底上依次制备PbTiO3（PT）、PZT，最后镀Al作为反射面，形成Si／Pr／PZT／Al的膜层结构。对制备完全的试片在数字波面干涉仪上进行了形变测试，尽管受到了薄膜热形变作用的影响，仍实现了约1．2μm的可控形变，证明该方案用做自适应变形反射镜的可行性。     

PT种子层对PZT薄膜结晶及压电性能的影响

采用溶胶-凝胶法(Sol-Gel)在Pt/Si衬底上制备了PbTiO3 (PT)薄膜和Pb (Zrx,Ti1-x)O3(PZT)薄膜,研究了退火温度以及PT种子层对PZT薄膜结晶及压电性能的影响。X射线衍射(XRD)结果表明,制备的PZT薄膜为纯钙钛矿结构的多晶薄膜,有PT种子层的PZT薄膜晶粒尺寸更大,(110)面取向度更高,结晶性能更好;原子力显微镜(AFM)结果表明,制备的薄膜表面形貌比较平整、均匀、无裂纹;压电力显微镜(PFM)结果表明,压电力显微镜(PFM)结果表明,有PT种子层时,PZT薄膜的平均压电系数d33为128～237 pm/V,无PT种子层时平均压电系数d33为21～29 pm/V。在升温速率为10 ℃/s的退火条件下保温10 min时,随着退火温度的升高,PZT薄膜晶粒尺寸增大,粗糙度增大,(110)面取向度升高,平均压电系数d33增大。PT种子层能够有效的改善PZT薄膜的结晶性能和压电性能。     

High‐Temperature BiScO3‐PbTiO3 Piezoelectric Vibration Energy Harvester

Conventionally, effective mechanical vibration energy harvesting is based on (Pb,Zr)TiO₃ (PZT) ceramics, poly(vinylidene fluoride) (PVDF) polymers or PVDF/PZT or other piezoelectric composite materials, and their working temperature is normally limited to room temperature (R‐T) or below 150 °C. Here, bismuth scandium lead titanate (BiScO₃‐PbTiO₃, abbreviated as BSPT) ceramic is reported which has a high Curie temperature point around 450 °C and its application for high‐temperature (H‐T) vibration energy harvesting. Experimental results show that it exhibits an excellent H‐T piezoelectricity, converting mechanical vibration energy into electric power effectively in a wide temperature range from R‐T till 250 °C. This research shows the BSPT piezoelectric energy harvester having the potential application for self‐power source of wireless sensor network system in high temperature circumstance.     

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.     

Wafer‐Scale Single‐Crystalline Ferroelectric Perovskite Nanorod Arrays

1D ferroelectric nanostructures are promising for enhanced ferroelectric and piezoelectric performance on the nanoscale, however, their synthesis at the wafer scale using industrially compatible processes is challenging. In order to advance the nanostructure‐based electronics, it is imperative to develop a silicon‐compatible growth technique yielding high volumetric density and an ordered arrangement. Here, a major breakthrough is provided in addressing this need and ordered and close‐packed single crystalline ferroelectric nanorod arrays, of composition PbZr_0.52Ti_0.48O₃ (PZT), grown on commercial grade 3 in. silicon wafer are demonstrated. PZT nanorods exhibit enhanced piezoelectric and ferroelectric performance compared to thin films of similar dimensions. Sandwich structured architecture utilizing 1D PZT nanorod arrays and 2D reduced graphene oxide thin film electrodes is fabricated to provide electrical connection. Combined, these results offer a clear pathway toward integration of ferroelectric nanodevices with commercial silicon electronics.     

用于微传感器中PZT压电薄膜的制备和图形化

采用溶胶-凝胶法在Si/Si3N4/Poly-Si/Ti/Pt基片上制备PZT压电薄膜, 为了选择更适合微电子机械系统(MEMS)器件的压电薄膜,采用一般热处理和快速热处理对锆钛酸铅(PZT)压电薄膜进行干燥和结晶.首先,采用V(H2O):V(HCL):V(HF)＝280 mL:120 mL:4drops(4滴HF溶液)配比的腐蚀液在室温下对未结晶的PZT压电薄膜进行了湿法腐蚀微细加工;然后,对图形化好的压电薄膜进行再结晶的热处理,实验结果表明这种方法可用于压电薄膜微器件的制备.     

Ferroelectric and Ferromagnetic Behavior of Pb(Zr0.52Ti0.48)O3–Co0.9Zn0.1Fe2O4 Multilayered Thin Films Prepared via Solution Processing

Multilayered multiferroic nanocomposite films of Pb(Zr_0.52Ti_0.48)O₃ (PZT) and Co_0.9Zn_0.1Fe₂O₄ (CZFO) are prepared on general Pt/Ti/SiO₂/Si substrates via a simple solution‐processing method. Structural characterization by X‐ray diffraction and electron microscopy techniques reveals good surface and cross‐sectional morphologies of these multilayered thin films. In particular, at room temperature strong ferroelectric and ferromagnetic responses are simultaneously observed in the multilayered thin films, depending on the deposited sequences and volume fractions of ferroelectric PZT phase and magnetic CZFO phase.     

Evaluation of PZT thin films on Ag coated Si substrates

Fabrication characteristics of hybrid thin film components are investigated. Lead zirconate titanate (PZT) films, thickness 10 μm, are fabricated by using laser ablation on the Ag electrode (about 1 μm thick) which is deposited on 200 μm Si substrates by evaporation. Composition close to the target material is obtained in PZT films even in air and without substrate heating. Low surface energy in the Ag−Si system causes spheroidization of the Ag layer on the fresh Si substrate, but the surface can be modified by grinding and oxidization. Only some cavities exist at the interface. The interface between the Ag electrode and PZT layer is physically continuous, as revealed by electron microscopy. After annealing at 750°C for 2 h, the PZT layer consists of the rhombohedral perovskite phase with a fraction of the pyrochlore phase. Detrimental interdiffusion between Pb and Si occurs during annealing if the PZT thin film is directly on the Si substrate. This is retarded by the presence of the Ag layer.     

用扫描压电显微术观察不同掺杂PZT薄膜的铁电畴分布

我们用扫描压电显微术，观察了未掺杂和掺La、Eu的PZT的铁电畴分布，结果表明：在自发极化下，用溶胶一凝胶法得到的PZT，(Pb0.93La0.07)(ti0.6ZR0.4)O3，(Pb0.95Eu0.05)(Zr0.52Ti0.48)O3和(Ph0.9Eu0.1)(Zr0.52Ti0.48)O3的表面铁电畴呈现较大的不同，掺La和掺Eu的样品均比未掺杂的有较大的自发极化。含Eu为5％时自发极化强度最高，且大部分畴界位置与晶界接近。通过改变加在探针上交变电压的幅值，观察铁电畴衬度的变化，可以看到，当交变电压升高时，某些畴变得不稳定，极化方向不同于自发极化，而衬度随交变电压线性增加，表明该区域晶粒在垂直方向贯通膜面，矫顽力高于外电场，且无明显的缺陷所致的压电性损失。     

Elastic Properties of 2D Ultrathin Tungsten Nitride Crystals Grown by Chemical Vapor Deposition

3D transition metal nitrides are well recognized for their good electrical conductivity, superior mechanical properties, and high chemical stability. Recently, 2D transition metal nitrides have been successfully prepared in the form of nanosheets and show potential application in energy storage. However, the synthesis of highly crystalline and well‐shaped 2D nitrides layers is still in demand for the investigation of their intrinsic physical properties. The present paper reports the growth of ultrathin tungsten nitride crystals on SiO₂/Si substrates by a salt‐assisted chemical vapor deposition method. High‐resolution transmission microscopy confirms the as‐grown samples are highly crystalline WN. The stiffness of ultrathin WN is investigated by atomic force microscopy–based nanoindentation with the film suspended on circular holes. The 3D Young's modulus of few‐layer (4.5 nm thick or more) WN is determined to be 3.9 × 10² ± 1.6 × 10² GPa, which is comparable with the best experimental reported values in the 2D family except graphene and hexagonal boron nitride. The synthesis approach presented in this paper offers the possibilities of producing and utilizing other highly crystalline 2D transition‐metal nitride crystals.