Low-temperature crystalline lead-free piezoelectric thin films grown on 2D perovskite nanosheet for flexible electronic device applications

A monolayer of Sr2Nb3Oio(SNO)is deposited on the Pt/Ti/SiCWSi(Pt?Si)or Pt/Ti/polyimide(Pt-Pl)substrate by using the Langmuir-Blodgett method and employed as a seed-layer for the growth of a crystalline(Nai_xKx)NbO3(NKN)film at 350℃.The crystalline NKN film is grown along the[001]direction on the SNO/Pt-Si(or SNO/Pt-PI)substrate.Due to the presence of oxygen vacancies in the SNO seed-layer,the NKN film exhibits low ferroelectric properties and large leakage current.To ameliorate these properties,the SNO/Pt-Si substrate is annealed in a 50 Torr oxygen atmosphere at 300℃,which removes the oxygen vacancies.Consequently,the NKN film deposited on this substrate exhibits promising electrical properties,namely a dielectric constant of 278,dissipation factor of 1.7%,a piezoelectric 8nstant of 175 pm`V^-1,and a leakage current density of 6.47 x 10^-7 A cm^-2 at-0.2 MV crrT1.Similar electrical properties are obtained from the NKN film grown on the flexible SNO/Pt-PI substrate at 350°C.Hence,the NKN films grown on the SNO seed-layer at 350°C can be applied to electronic devices with flexible polymer substrates.

Research of Lead-free Na_(0.5)Bi_(0.5)TiO_(3)-BaTiO_(3)System Piezoelectric Ceramics

To reduce the coercive field of Na_(0.5)Bi_(0.5)TiO_(3),Ba TiO_(3)were added as dopant materials.Then the(1-x)Na_(0.5)Bi_(0.5)TiO_(3)-xBaTiO_(3)ceramic samples were produced in solid synthetic way.The optimum preparation condition and piezoelectric properties of the samples were investigated.The XRD results show that the fabric transites from rhombohedral to tetragonal gradually with the substitution of the Ba^(2+).The morphotropic phase boundaries(MPB)exists in the composition range of 0.06.

Manufacture and Cytotoxicity of a Lead-free Piezoelectric Ceramic as a Bone Substitute—Consolidation of Porous Lithium Sodium Potassium Niobate by Cold Isostatic Pressing

Aim The piezoelectric properties and cytotoxicity of a porous lead-free piezoelectric ceramic for use as a direct bone substitute were investigated. Methodology Cold isostatic pressing （CIP） was applied to fabricate porous lithium sodium potassium niobate （Li0.06Na0.5K0.44） NbO3 specimens using a pore-forming method. The morphologies of the CIP-processed specimens were characterized and compared to those of specimens made by from conventional pressing procedures. The effects of the ceramic on the attachment and proliferation of osteoblasts isolated from the cranium of 1-day-old Sprague- Dawley rats were examined by a scanning electron microscopy （SEM） and metbylthiazol tetrazolium （MTT） assay. Results The results showed that CIP enhanced piezoelectricity and biological performance of the niobate specimen, and also promoted an extracellular matrix-like topography of it. In vitro studies showed that the CIP-enhanced material had positive effects on the attachment and proliferation of osteoblasts. Conclusion Niobate ceramic generated by CIP shows a promise for being a piezoelectric composite bone substitute.

Effect of Li content on the microstructure and properties of lead-free piezoelectric(K_(0.5)Na_(0.5))_(1-x)Li_xNbO_3 ceramics prepared by SPS

Lead-free piezoelectric （K0.5sNa0.5）1-xLixNbO3 （x = 0at%-20at%） ceramics were synthesized by spark plasma sintering （SPS） at low temperature and the effects of LiNbO3 addition on its crystal structure and properties were also studied. When the Li content was less than 6at%, a single proveskite phase with the similar structure of （K0.5Na0.5）NbO3 was formed; and a secondary phase with K3Li2Nb5O15 structure was observed in the 6at% 〈 x 〈 20at% compositional range. Furthermore, LiNbO3 existed as the third phase when the Li content was higher than 8at%. The grain sizes increased from 200-500 nm to 5-8 μm when the K3Li2Nb5O15 and LiNbO3 like phases were formed. With increasing Li content, the relative density of the ceramics first decreased from 97% to 93% and then kept constant. The piezoelectric coefficient d33, dielectric constant, and planner electromechanical coupling factor exhibited a decreasing tendency with increasing Li content because of the decrease in density and the formation of the secondary phase such as K3Li2Nb5O15 and LiNbO3. The formation of dense microstructure with a single phase is necessary in improving the properties of the （K0.5Na0.5）1-xLixNbO3 ceramics.

Preparation and Piezoelectric Properties of CuO-added(Ag_(0.75)Li_(0.1)Na_(0.1)K_(0.05_)NbO_3 Lead-free Ceramics

CuO-doped（Ag0.75Li0.1Na0.1K0.05）NbO3（ALNKN-xCuO, x = 0.2mol%） lead-free piezoelectric ceramics were prepared by the solid-state reaction method in air atmosphere. The effects of CuO addition on the phase structure, microstructure, and piezoelectric properties of the ceramics were investigated. The experimental results show that the ALNKN ceramics without doping CuO possess rhombohedral phase along with K2NbrO16- type phase and metallic silver phase. For all of the CuO-doped ALNKN ceramics, a pure perovskite structure with the orthorhombic phase was obtained by enclosing the samples in a corundum tube. A homogeneous microstructure with＇the grain size of about 1 ~tm was formed for the ceramics with 0.5mo1% CuO. The grain size increases with increasing amount of CuO. The temperature dependence of dielectric properties indicates that the ferroelectric phase of the ALNKN-xCuO ceramics becomes less stable with the addition of CuO. The ceramics with x = lm01% exhibit relatively good electrical properties along with a high Curie temperature. These results will provide a helpful guidance to preparing other AN-based ceramics by solid-state reaction method in air atmosphere.

Microstructure and electrical properties of Ti-modified (Na_(0.5)K_(0.5))(Ti_xNb_(1-x))O_3 lead-free piezoelectric ceramics

Ti-Modified (Na0.5K0.5)(TixNb1-x)O3 (NKNT) piezoelectric ceramics were fabricated by double-layer buried powder process at 1020°C for 2 h. The microstructures,and piezoelectric and dielectric properties of the lead-free NKNT ceramics were investigated. X-ray diffraction re-sults indicated that Ti4+ had diffused into the (Na0.5K0.5)NbO3 lattices to form a solid solution with a perovskite structure. The introducing of Ti into the (Na0.5K0.5)NbO3 solid solution effectively reduced the sintering temperature and densified the microstructure with a decreased grain size. The highest relative density reached more than 90%. The highest piezoelectric dielectric coefficient d33 and planar mode electro-mechanical coupling coefficient kp were 110 pC/N and 19.5%,which were obtained in the NKNT ceramic with 1 mol% Ti. The piezoelectric properties of the NKNT ceramics were enhanced by aging in air for a period of time owing to the compensation of oxygen vacancies.

Synthesis and Piezoelectric Properties of Lead-free (Bi_(0.5)Na_ (0.5))_ 1-x(Ba_aSr_b)_xTiO_3 Ceramics

A new group of lead-free piezoelectric ceramics,（Bi0.5 Na0.5）1-x（BaaSrb）xTiO3（abbreviated as BNBST[100x-100a/100b],0〈x〈1,a＋b=1）,was synthesized.The ceramics were prepared by conventional ceramic sintering technique,and the ceramics with density of 95% of the theoretical one can be sintered without the atmosphere control during the sintering process.The results of the X-ray diffraction（XRD） data show that the ceramics possess a single perovskite phase.The measurements of dielectric and piezoelectric properties reveal that the ceramics provide relatively high piezoelectric charge constant d33 and high planar electromechanical coupling factor kp.For the BNBST6-95/5 ceramics,d33 is equal to 170pC/N,and kp is equal to 32.0%.The fabrication technique for these ceramics is conventional and stable.

Surface Acoustic Wave Humidity Sensors Based on(1120) ZnO Piezoelectric Films Sputtered on R-Sapphire Substrates

ZnO films on R-sapphire substrates are prepared and characterized by x-ray diffraction and scanning electron microscopy, which indicate that the thin films are well crystallized with （1120） texture. Love wave and Rayleigh wave are used for fabrications of humidity sensors, which are excited in [1100] and [0001] directions of the （1120） ZnO piezoelectric films, respectively. The experimental results show that both kinds of sensors have good humidity response and repeatability, and the performances of the Love wave sensors are better than those of the Rayleigh wave sensors at room temperature. Moreover, the theoretical calculations of the mass sensitivity of the sensors are a/so carried out and the calculated results are in good agreement with the experimental measurements.

Characterization of La-doped xBiInO_3(1-x)PbTiO_3 Piezoelectric Films Deposited by the Radio-Frequency Magnetron Sputtering Method

La-doped and undoped xBiIn03-（1 - x）PbTi03 （BI-PT） thin films are deposited on （101）SrRuO3/（lOO）Pt/（lO0） MgO substrates by the rf-magnetron sputtering method. The structures of the films are characterized by XRD and SEM, and the results indicate that the thin films are grown with mainly （100） oriented and columnar structures. The ferroelectricity and piezoelectricity of the BI-PT films are also measured, and the measured results illustrate that both performances are effectively improved by the La-doping with suitable concentrations. These results will open up wide potential applications of the films in electronic devices.

Effects of Na/K ratio on the phase structure and electrical properties of Na_xK_(1-x)NbO_3 lead-free piezoelectric ceramics

Lead-free piezoelectric NaxK1-xNbO3（x = 0.3-0.8）（NKN） ceramics were fabricated by normal sintering at 1060°C for 2 h.Microstructures and electrical properties of the ceramics were investigated with a special emphasis on the influence of Na content.The grain size of the produced dense ceramic was decreased by increasing Na content.A discontinuous change in the space distance was found at the composition close to Na0.7K0.3NbO3 ceramic, which indicates the presence of a transitional composition between two different orthorhombic phases, which is similar to the behavior of morphotropic phase boundary（MPB） in NaxK1-xNbO3 ceramics.Such MPB-like behavior contributes to the enhanced piezoelectric coefficient d33 of 122 pC/N, planar-mode electromechanical coupling coefficient kP of 28.6%, and dielectric constant εr of 703, respectively for the Na0.7K0.3NbO3 ceramic.Cubic temperature TC and the transitional temperature TO-T from orthorhombic to tetragonal phase are observed at around 420°C and 200°C, respectively.

Microstructures and Electrical Properties of Bi_(0.5)-(Na_(1-x-y)K_xLi_y)_(0.5)TiO_3 Lead-free Piezoelectric Ceramics

The microstructures and electrical properties of Bi0.5（Na1-x-yKxLiy）0.5TiO3 lead-free piezoelectric ceramics were studied.These ceramics were prepared by conventional ceramic technique.XRD analysis reveals that the ceramics possess almost pure perovskite phase when y≤0.2.The SEM results show that,with more amounts of Li＋,the crystalline grain growing speed is accelerated,and the sintering temperature can effectively be decreased.The measurements of piezoelectric properties indicate that the ceramics with relatively low amount of Li＋ and high amount of K＋ have comparatively large piezoelectricity.The dielectric measurements show that the ceramics have properties like relaxor ferroelectrics and diffuse phase transition（DPT） at Td and Tc,respectively.The results of ferroelectric measurements reveal the system has relatively higher remanent polarization Pr（27.6 μC/cm2） and lower coercive field Ec（37.5 kV/cm）.

Effects of A-site non-stoichiometry on the structural and electrical properties of 0.96K_(0.5)Na_(0.5)NbO_3-0.04LiSbO_3 lead-free piezoelectric ceramics

Effects of A-site non-stoichiometry on the structural and electrical properties of 0.96K0.5＋xNa0.5＋xNbO3- 0.04LiSbO3 lead-free piezoelectric ceramics were examined for 0 ≤ x ≤0.02. The piezoelectric coefficients exhibited a maximum, d33 = 187 pC/N at x = 0.0075, coinciding with the maximum of the grain size and the apparent density at x = 0.0075. The apparent density and the piezoelectric coefficients decreased with increasing x at higher x which was likely due to the crystal geometrical distortion of 0.96K0.5＋xNa0.5＋xNbO3-0.04LiSbO3. In addition, super-large grains were found and this may be due to liquid phase sintering. Excess （K＋＋Na＋） attracted a sum of space charges to keep the charge neutral, resulting in charge leakage during the course of ceramic polarization, influencing the piezoelectric and ferroelectric properties. These findings are of importance for guiding the design of Ko.sNao.sNbO3-based lead-free ceramics with enhanced electrical properties.

Enhanced Ferroelectric and Converse Piezoelectric Properties of Dense Lead-Free Na_0.4K_0.1Bi_0.5TiO₃Ceramics for Actuator Applications

In this work, lead-free Na0.4Bi0.5 TiO3-K0.1Bi0.5TiO3 (NKBT) piezoelectric ceramics were prepared by the solid-state reaction method and their structural, ferroelectric and dielectric properties were systematically studied. NKBT sintered at 1150℃ for 4 h exhibited highly dense (96% - 98% of the theoretical density) and uniform grains of size 1.1 μm. The coexistence of tetragonal (P4bm) and rhombohedral (R3c) phases due to the presence of morphotrophic phase boundary for the chosen composition has been confirmed by the Rietveld refinement studies. Enhanced ferroelectric properties such as remnant polarization (Pr) and coercive field (EC) are found to be 37 μC/cm2 and 30 kV/cm, respectively. The optimized synthesis procedure for NKBT ceramics resulted in enhanced strain (%) and converse piezoelectric coefficient (d33*) of 0.3 % and 554 pm/V which is attributed to smaller grain size and switching of non 180o domains. NKBT ceramics with such excellent piezoelectric properties can be considered as a promising candidate for actuator applications.

Orientation dependence on piezoresponse of lead-free piezoelectric sodium bismuth titanate epitaxial thin films

Lead-free piezoelectric sodium bismuth titanate((Bi0.5Na0.5)TiO3,BNT)thin films were epitaxially grown onto(001)-,(110)-,and(111)-oriented Nb:SrTiO3(STO)single crystal substrates prepared by sol-gel processing.Highly oriented growth in(001),(110),and(111)BNT thin films was obtained in this work benefiting from the lattice match between the BNT film and the STO substrate.The different growth models in thin films with various orientations result in various surface morphologies dependent on the film orientation.The piezoresponse of the BNT thin films was represented exhibiting a strong orientation dependence that(110)>(001)>(111).This is contributed by the various domain switching contribution related to the crystal symmetry and polarization distribution in the three oriented thin films.

BIMORPH-TYPE PIEZOELECTRIC THIN FILM BENDING ACTUATORS SYNTHESIZED BY HYDROTHERMAL METHOD

Lead zirconate titanium solid-solution (PZT) thin films with variousthickness are synthesized on titanium substrates by repeated hydrothermal treatments. Young modulus,electric-field-induced displacement and the density of the PZT film are measured respectively.Bimorph- type bending actuators are fabricated using these films. The model, which is used toanalyze the driving ability of bimorph-type bending actuators by hydrothermal method, is set up. Itcan be seen that the driving ability of bimorph-type bending actuators can be greatly improved byoptimizing the thickness of PZT thin film and substrate from the theoretical analysis results. Themeasured values are expected to agree with the theoretical values calculated by the above model.

Ferroelectric and piezoelectric properties of lead-free Li_(0.06)(K_(0.5)Na_(0.5))_(0.94)NbO_(3) thin films

Lead-free(K_(0.5)Na_(0.5))NbO_(3)(KNN)and Li_(0.06)(K_(0.5)Na_(0.5))_(0.94)NbO_(3)(LKNN)thin films were fabricated by a sol-gel method.The effects of Li substitution on crystal structure,microstructure and electrical properties of KNN film were systematically studied.Li doping can enhance the ferroelectric and piezoelectric properties of KNN film.Compared with pure KNN film,the LKNN film possesses larger remanent polarization(P_(r)~9.3μC/cm^(2))and saturated polarization(P_(s)~41.2μC/cm^(2))and lower leakage current density(~10^(−5)A/cm^(2)at 200 kV/cm).Meanwhile,a typical butterfly shaped piezoelectric response curve is obtained in the LKNN film with a high piezoelectric coefficient(d_(33)~105 pm/V).Excellent fatigue resistance(~10^(9)switching cycles)and aging resistance(~180 days)demonstrate the long-term working stability of LKNN film.These findings indicate that KNN-based lead-free piezoelectric films have a broad application prospect in microelectromechanical systems(MEMS).

Stoney formula for piezoelectric film/elastic substrate system

With the trends in miniaturization, and particularly the introduction of micro- and nano-electro-mechanical system, piezoelectric materials used in microelectronic devices are deposited usually in the form of thin film on elastic substrates. In this work, the bending of a bilayer comprising a piezoelectric film deposited on an elastic substrate, due to the mismatch, is investigated. An analytic formula relating the curvature of the bilayer to the mismatch, the electroelastic constants and the film thickness is obtained, and from this formula, a transverse piezoelectric constant d31 can be estimated. Meanwhile the influence of electrornechanical coupling coefficient on the curvature is discussed.

Performance of beam-type piezoelectric vibration energy harvester based on ZnO film fabrication and improved energy harvesting circuit

We demonstrate a piezoelectric vibration energy harvester with the ZnO piezoelectric film and an improved synchronous electric charge extraction energy harvesting circuit on the basis of the beam-type mechanical structure,especially investigate its output performance in vibration harvesting and ability to generate charges.By establishing the theoretical model for each of vibration and circuit,the numerical results of voltage and power output are obtained.By fabricating the prototype of this harvester,the quality of the sputtered film is explored.Theoretical and experimental analyses are conducted in open-circuit and closed-circuit conditions,where the open-circuit mode refers to the voltage output in relation to the ZnO film and external excitation,and the power output of the closed-circuit mode is relevant to resistance.Experimental findings show good agreement with the theoretical ones,in the output tendency.It is observed that the properties of ZnO film achieve regularly direct proportion to output performance under different excitations.Furthermore,a maximum experimental power output of 4.5 mW in a resistance range of 3 kΩ-8 kΩis achieved by using an improved synchronous electric charge extraction circuit.The result is not only more than three times the power output of classic circuit,but also can broaden the resistance to a large range of 5 kΩunder an identical maximum value of power output.In this study we demonstrate the fundamental mechanism of piezoelectric materials under multiple conditions and take an example to show the methods of fabricating and testing the ZnO film.Furthermore,it may contribute to a novel energy harvesting circuit with high output performance.