力电多场鼓包法测定PZT铁电薄膜的横向压电系数

为表征Pb(Zr_(0.52)Ti_(0.48))O_3(PZT)薄膜的横向压电性能,以纯力场鼓包测试模型和铁电薄膜材料压电方程为基础,推导了PZT铁电薄膜的力电耦合鼓包本构模型。采用溶胶-凝胶法制备了PZT铁电薄膜,并通过化学腐蚀法获得PZT薄膜鼓包样品。在外加电压为0~14V的条件下进行鼓包测试。结果表明,在纯力场作用下,PZT薄膜的弹性模量和残余应力分别为91.9GPa和36.2MPa;随着电压从2V变化到14V,PZT薄膜的横向压电系数d31从-28.9pm/V变化到-45.8pm/V。本工作所发展的力电耦合鼓包测试技术及力电耦合鼓包本构模型为评价铁电薄膜材料的横向压电性能提供了一种有效的分析方法。     

Highly polarized single-c-domain single-crystal Pb(Mn,Nb)O(3)-PZT thin films

In-plane unstrained single-c-domain/single-crystal thin films of PZT-based ternary ferroelectric perovskite, ξPb(Mn,Nb)O3-(1 - ξ)PZT, were grown on SrRuO(3)/Pt/MgO substrates using magnetron sputtering followed by quenching. The sputtered unstrained thin films exhibit unique ferroelectric properties: high coercive field, Ec > 180 kV/cm, large remanent polarization, P(r) = 100 μC/cm(2), small relative dielectric constants, ε* = 100 to 150, high Curie temperature, Tc = ~600 °C, and bulk-like large transverse piezoelectric constants, e31,f = -12.0 C/m(2) for PZT(48/52) at ξ = 0.06. The unstrained thin films are an ideal structure to extract the bulk ferroelectric properties. Their micro-structures and ferroelectric properties are discussed in relation to the potential applications for piezoelectric MEMS.     

Characterization of sol-gel Pb(Zr0.53Ti0.47O3) in thin film bulk acoustic resonators

The behavior of {f111g}-textured Pb(Zr(0.53Ti0.47O3) (PZT) deposited by the sol-gel technique in thin film bulk acoustic resonators (TFBAR's) was investigated at a resonance frequency of about 1 GHz. The resonators were fabricated on Si wafers using deep silicon etching to create a membrane structure and using platinum as top and bottom electrodes. The best response of the resonators was observed at a bias voltage of -15 kV/cm with values of about 10% for the coupling constant and about 50 for the quality factor. This voltage corresponds to optimal values of piezoelectric constant d33 and dielectric constant measured as a function of the electric field. The influence of a bias voltage on the resonance frequency, antiresonance frequency, and coupling constant were observed. Both the resonance and antiresonance frequency show a hysteretic change with applied bias. This effect can be used to shift the whole band of a filter by applying a voltage. The TFBAR structure also allowed us to extract values for materials parameters of the PZT film. Dielectric, piezoelectric, and elastic properties of the f111g-textured PZT film are reported and compared to direct measurements and to literature values.     

Fabrication and modeling of high-frequency PZT composite thick film membrane resonators

High-frequency, thickness mode resonators were fabricated using a 7 microm piezoelectric transducer (PZT) thick film that was produced using a modified composite ceramic sol-gel process. Initial studies dealt with the integration of the PZT thick film onto the substrate. Zirconium oxide (ZrO2) was selected as a diffusion barrier layer and gave good results when used in conjunction with silicon oxide (SiO2) as an etch stop layer. Using these conditions, devices were produced and the acoustic properties measured and modeled. The resonators showed a resonant frequency of about 200 MHz, an effective electromechanical coupling coefficient of 0.34, and a Q factor of 22. Modeling was based on a Mason-type model that gave good agreement between the experimental data and the simulations. The latter showed, for the PZT thick film, an electromechanical coupling coefficient of 0.35, a stiffness of 8.65 x 10(10) N x m(-2) and an e33,f piezoelectric coefficient of 9 C x m(-2).     

Fabrication and characterization of micromachined high-frequency tonpilz transducers derived by PZT thick films

Miniaturized tonpilz transducers are potentially useful for ultrasonic imaging in the 10 to 100 MHz frequency range due to their higher efficiency and output capabilities. In this work, 4 to 10-microm thick piezoelectric thin films were used as the active element in the construction of miniaturized tonpilz structures. The tonpilz stack consisted of silver/lead zirconate titanate (PZT)/lanthanum nickelate (LaNiO3)/silicon on insulator (SOI) substrates. First, conductive LaNiO3 thin films, approximately 300 nm in thickness, were grown on SOI substrates by a metalorganic decomposition (MOD) method. The room temperature resistivity of the LaNiO3 was 6.5 x 10(-6) omega x m. Randomly oriented PZT (52/48) films up to 7-microm thick were then deposited using a sol-gel process on the LaNiO3-coated SOI substrates. The PZT films with LaNiO3 bottom electrodes showed good dielectric and ferroelectric properties. The relative dielectric permittivity (at 1 kHz) was about 1030. The remanent polarization of PZT films was larger than 26 microC/cm2. The effective transverse piezoelectric e31,f coefficient of PZT thick films was about -6.5 C/m2 when poled at -75 kV/cm for 15 minutes at room temperature. Enhanced piezoelectric properties were obtained on poling the PZT films at higher temperatures. A silver layer about 40-microm thick was prepared by silver powder dispersed in epoxy and deposited onto the PZT film to form the tail mass of the tonpilz structure. The top layers of this wafer were subsequently diced with a saw, and the structure was bonded to a second wafer. The original silicon carrier wafer was polished and etched using a Xenon difluoride (XeF2) etching system. The resulting structures showed good piezoelectric activity. This process flow should enable integration of the piezoelectric elements with drive/receive electronics.     

PZT薄膜的MOCVD制备技术

采用直接液体榆运-金属有机化合物化学气相沉积技术（DLI-MOCVD）制备Pb（ZrxTi1-x）O3薄膜（PZT薄膜）,并进行了相关研究,通过调节MOCVD中影响PZT质量的主要工艺参数（温度、压力、系统的气体（Ar,O2）流量、衬底转速、蠕动泵速）,制备不同组分PZT薄膜（均匀性≥±95％,尺寸为2．54—20．32cm（1—8in）,厚度为50—500nm）．经XRD测试可见,PZT薄膜已形成钙钛矿结构．用SEM对其表面进行分析,结果表明,PZT薄膜表面致密均匀．     

High frequency piezoelectric MEMS ultrasound transducers

High-frequency ultrasound array transducers using piezoelectric thin films on larger structures are being developed for high-resolution imaging systems. The increase in resolution is achieved by a simultaneous increase in operating frequency (30 MHz to about 1 GHz) and close coupling of the electronic circuitry. Two different processing methods were explored to fabricate array transducers. In one implementation, a xylophone bar transducer was prototyped, using thin film PbZr(0.52)Ti(0.48)O(3) (PZT) as the active piezoelectric layer. In the other, the piezoelectric transducer was prepared by mist deposition of PZT films over electroplated Ni posts. Because the PZT films are excited through the film thickness, the drive voltages of these transducers are low, and close coupling of the electronic circuitry is possible. A complementary metal-oxidesemiconductor (CMOS) transceiver chip for a 16-element array was fabricated in 0.35-microm process technology. The ultrasound front-end chip contains beam-forming electronics, receiver circuitry, and analog-to-digital converters with 3-Kbyte on-chip buffer memory.     

Surface acoustic wave characteristics and electromechanical coupling coefficient of lead zirconate titanate thin films

Lead zirconate titanate (PZT) thin films were created on ST-X quartz using radio frequency magnetron sputtering deposition. PZT films deposited on quartz are used as a new piezoelectric substrate for surface acoustic wave (SAW) devices. Microelectromechanical technique was used to fabricate interdigital transducers on the surface of the substrate to be used as a SAW delay line device. The results show that the PZT film was successfully deposited on ST-X quartz, and that the PZT film on ST-X quartz can enhance the electromechanical coupling coefficients of SAW.     

Theory and operation of 2-D array piezoelectric micromachined ultrasound transducers

Piezoelectric micromachined ultrasound transducers (pMUTs) are a new approach for the construction of 2-D arrays for forward-looking 3-D intravascular (IVUS) and intracardiac (ICE) imaging. Two-dimensional pMUT test arrays containing 25 elements (5 x 5 arrays) were bulk micromachined in silicon substrates. The devices consisted of lead zirconate titanate (PZT) thin film membranes formed by deep reactive ion etching of the silicon substrate. Element widths ranged from 50 to 200 ?m with pitch from 100 to 300 ?m. Acoustic transmit properties were measured in de-ionized water with a calibrated hydrophone placed at a range of 20 mm. Measured transmit frequencies for the pMUT elements ranged from 4 to 13 MHz, and mode of vibration differed for the various element sizes. Element capacitance varied from 30 to over 400 pF depending on element size and PZT thickness. Smaller element sizes generally produced higher acoustic transmit output as well as higher frequency than larger elements. Thicker PZT layers also produced higher transmit output per unit electric field applied. Due to flexure mode operation above the PZT coercive voltage, transmit output increased nonlinearly with increased drive voltage. The pMUT arrays were attached directly to the Duke University T5 Phased Array Scanner to produce real-time pulse-echo B-mode images with the 2-D pMUT arrays.     

Fabrication of 3-dimensional PbZr(1-x)Ti(x)O3 nanoscale thin film capacitors for high density ferroelectric random access memory devices

PbZr(x)Ti(1-x)O3 (PZT) thin films were deposited on 3-dimensional (3D) nano-scale trench structures for use in giga-bit density ferroelectric random access memories. PZT thin films were deposited by liquid delivery metalorganic chemical vapor deposition using Pb(thd)2, Zr(MMP)4, and Ti(MMP)4 precursors dissolved in ethyl cyclohexane. Iridium thin films were deposited by atomic layer deposition, and they exhibited excellent properties for capacitor electrodes even at a thickness of 20 nm. The trench capacitor was composed of three layers, viz. Ir/PZT/lr (20/60/20 nm), and had a diameter of 250 nm and a height of 400 nm. Almost 100% step coverage was obtained at a deposition temperature of 530 degrees C. The PZT thin film capacitors with a thickness of 60 nm on a planar structure exhibited a remnant polarization (Pr) of 28 microC/cm2, but the Pr value of the 3D PZT capacitors decreased slightly with decreasing 3D trench pattern size. The transmission electron microscope analysis indicated that the PZT thin films had compositional uniformity in the 3D trench region. Both columnar and granular grains were formed on the sidewalls of the trench capacitors, and their relative proportion exhibited strong size dependence. The trench capacitors with more columnar PZT grains showed good switching behavior under an external bias of 2.1 V and had a remnant polarization of 19-24 microC/cm2.     

Epitaxial growth and electrical measurement of single crystalline Pb(Zr0.52Ti0.48)O3 thin film on Si(001) for micro-electromechanical systems

We report in this work the epitaxial growth and the electrical characteristics of single crystalline Pb(Zr_0.52Ti_0.48)O₃ (PZT) thin film on SrTiO₃(STO)-buffered Si(001) substrate. The STO buffer layer deposited by molecular beam epitaxy allows a coherent oxide/Si interface leading enhanced PZT crystalline quality. 70 nm-thick PZT (52:48) layer was then grown on STO/Si(001) by sol-gel method. X-ray diffraction demonstrates the single crystalline PZT film on Si substrate in the following epitaxial relationship: [110] PZT (001)//[110] STO (001)//[100] Si (001). The macroscopic electrical measurements show a hysteresis loop with memory window of 2.5 V at ± 7 V sweeping range and current density less than 1 μA/cm² at 750 kV/cm. The artificial domains created by piezoresponse force microscopy with high contrast and non-volatile properties provide further evidence for the excellent piezoelectric properties of the single crystalline PZT thin film.     

Self-separated PZT thick films with bulk-like piezoelectric and electromechanical properties

Self-separated Pb(Zr(0.52)Ti(0.48))O(3) (PZT) films were processed by a hydrothermal deposition and a rapid thermal separation method, followed by a sol-gel filling and sintering process. The films possess excellent piezoelectric and electromechanical properties close to those of bulk material. The maximum remnant polarization is over 30 μC/cm(2) and the electromechanical coupling factor (k(t)) reaches as high as 0.52. The unique microstructure characteristics of the PZT films, such as their highly dense structure, columnar grains, well-connected grain boundaries, and well-dispersed nanopores, could all contribute to the enhanced piezoelectric and electromechanical properties.     

Preparation and characterization of preferred oriented PZT films on amorphous substrates

The (001) preferred orientation of Nb-doped Pb(Zr_0.52Ti_0.48) O₃ (PZT) thin films was successfully realized on amorphous glass substrate with LaNiO₃(LNO) as electrode by rf-sputtering method. It was found that the LNO film greatly promotes formation of the PZT film with pervoskite phase on amorphous substrate and the preferred orientation of the PZT film depends strongly on the process of preparation. The experimental results show that the dielectric constant and loss of the PZT films with the (001) preferred orientation are 1308 and 0.042, respectively, at 1 kHz, 0.05 V. The remanent polarization (P_r), saturation polarization (P_s) and coercive field (E_c) are 34.5, 43 C/cm² and 105 kV/cm, respectively. The PZT films also show a 33 kV/cm internal bias field due to its (001) preferred orientation. The piezoelectric coefficient d₃₃ of the PZT film without the poled treatment is about 15 pC/N due to its (001) preferred orientation. The effect of the foreign stress on the piezoelectric voltage response of the PZT/LNO/glass was investigated. The results make us consider using the PZT film as an artificial skin to realize the self-diagnosis of amorphous materials under the action of stress.     

Comparative investigating the properties of Pb-based multilayer ferroelectric thin films for FeRAM

The PbZr_0.3Ti_0.7O₃(PZT) thin film and multilayer PbZr_0.3Ti_0.7O₃/PbTiO₃(PZT/PT), PbTiO₃/PbZr_0.3Ti_0.7O₃/ PbTiO₃(PT/PZT/PT) thin films were prepared by a Sol-Gel method on the Pt(111)/Ti/SiO₂/Si(100) substrate for FeRAM application. The microstructure, ferroelectric, fatigue, dielectric, and leakage current properties of these thin films were investigated. The results indicate that the multilayer PT/PZT/PT thin film have a better ferroelectric, fatigue, dielectric and leakage current density properties. Its remanent polarization P_r reaches a maximum value of 21.2 μC/cm² and the coercive field E_c gets to a minimum value of 64.2kV/cm. After 10¹⁰ cycles, it still has more than 80% remnant polarization. The PT/PZT/PT thin film exhibits lower dielectric constant and lower dielectric loss, which is beneficial for FeRAM application. It also has the lowest leakage current density. The leakage current mechanism of the PZT, PZT/PT and PT/PZT/PT thin films is correlated to the microstructure and can be modeled in terms of GBLC and SCLC theory. The microstructure and electric properties of these films are correlated. The double-sided PT seed layers enhance not only the microstructure but also the electric properties. It is evident that the PT/PZT/PT multilayer thin film is a promising candidate for FeRAM application.     

Thickness dependence of electrical properties of PZT films deposited on metal substrates by laser-assisted aerosol deposition

Dependence of electrical properties-dielectric, ferroelectric, and piezoelectric properties-on film thickness was studied for lead-zirconate-titanate (PZT) thick films directly deposited onto stainless-steel (SUS) substrates in actuator devices by using a carbon dioxide (CO₂), laser-assisted aerosol deposition technique. Optical spectroscopic analysis data and laser irradiation experiments revealed that absorption at a given wavelength by the film increased with increasing film thickness. Dielectric constant epsiv, remanent polarization value P_r, and coercive field strength E_c of PZT films directly deposited onto a SUS-based piezoelectric actuator substrate annealed by CO₂ laser irradiation at 850degC improved with increasing film thickness, and for films thicker than 25 mum, e > 800, Pr > 40 muC/cm², and E_c < 45 kV/cm. In contrast, the displacement of the SUS-based actuator with the laser-annealed PZT thick film decreased with increasing film thickness.     

Piezoelectric micromachined ultrasonic transducers: modeling the influence of structural parameters on device performance

Piezoelectric micromachined ultrasonic transducers (pMUTs), a potential alternative for conventional one-dimensional phased array ultrasonic transducers, were investigated. We used a modeling approach to study the performance of lead zirconate titanate (PZT)-driven pMUTs for the frequency range of 2-10 MHz, optimized for maximum coupling coefficient, as a function of device design. Using original tools designed for the purpose, a comprehensive build-test finite element model was developed to predict and measure the device performance. In particular, the model estimates the device coupling coefficient and the acoustic impedance, besides the readily extractable resonance frequency and bandwidth. To validate the model, a prototype device was built and tested, showing good agreement between the model predictions and experimental results. Modeling results indicate that the coupling coefficient is significantly affected by silicon membrane, PZT, and top electrode thickness as well as the top electrode design. Results also indicate considerable flexibility in maximizing the coupling coefficient while maintaining the device acoustic impedance at a level matching that of the human body. The bandwidth proved to be superior to that of conventional transducers, reaching 102% in some cases.     

Piezoelectric properties of PZT films prepared by the sol-gel method and their application in MEMS

Pb(Zr_0.52Ti_0.48)O₃ (PZT) piezoelectric thin films with thickness of 0.7-2.2 μm were prepared on Pt/Ti-coated SiO₂/Si (0.5 μm/300 μm) substrates by the sol-gel method. The piezoelectric coefficient e₃₁ of the PZT thin film was − 12.5 ± 0.3 C/m², which is evaluated by measuring the tip displacement of PZT-coated cantilevers of the dimensions 50 mm long, 4 mm wide, and 0.3 mm thick. The prepared PZT films demonstrated excellent piezoelectric properties and have large potential applications in MEMS devices. Micro-machined ultrasonic sensors, in which PZT-coated membrane functioned as sensing element, were fabricated and their properties were also characterized.     

Enhanced ferro- and piezoelectric properties in (100)-textured Nb-doped Pb(ZrxTi1 − x)O3 films with compositions at morphotropic phase boundary

To develop high-performance piezoelectric films on conventional Pt(111)/Ti/SiO₂/Si(100) substrates, sol-gel-derived highly [100]-textured Nb-doped Pb(Zr_xTi_1 − x)O₃ (PNZT) thin films with different Zr/Ti ratios ranging from 20/80 to 80/20 were prepared and characterized. The phase structure, ferroelectric and piezoelectric properties of the PZNT films were investigated as a function of Zr/Ti ratios, and it was confirmed that there was distinct phase transition of the PNZT system from tetragonal to rhombohedral when the Zr/Ti ratio varied across the morphotropic phase boundary (MPB). The Nb-doped PZT films showed enhanced remanent polarization but reduced coercive field, whose best values reached 75 μC/cm² and 82 kV/cm, respectively at the composition close to MPB. In addition, the [100]-textured PNZT film at MPB also shows a high piezoelectric coefficient up to 161 pm/V. All these properties are superior to those for undoped PZT films.     

Flexible highly-effective energy harvester via crystallographic and computational control of nanointerfacial morphotropic piezoelectric thin film

Controlling the properties of piezoelectric thin films is a key aspect for designing highly effident flexible electromechanical devices.In this stud~ the crystallographic phenomena of PbZr1-xTixO3 (PZT) thin films caused by distinguished interfacial effects are deeply investigated by overlooking views,including not only an experimental demonstration but also ab initio modeling.The polymorphic phase balance and crystallinity,as well as the crystal orientation of PZT thin films at the morphotropic phase boundary (MPB),can be stably modulated using interfacial crystal structures.Here,interactions with MgO stabilize the PZT crystallographic system well and induce the texturing influences,while the PZT film remains quasi-stable on a conventional Al2O3 wafer.On the basis of this fundamental understanding,a high-output flexible energy harvester is developed using the controlled-PZT system,which shows significantly higher performance than the unmodified PZT generator.The voltage,current,and power densities are improved by 556％,503％,and 822％,respectively,in comparison with the previous flexional single-crystalline piezoelectric device.Finally,the improved flexible generator is applied to harvest tiny vibrational energy from a real traffic system,and it is used to operate a commercial electronic unit.These results clearly indicate that atomic-scale designs can produce significant impacts on macroscopic applications.     

Fabrication of single crystal PZT thin films on glass substrates

 We have successfully transferred heteroepitaxial Pb(Zr,Ti)O₃ (PZT) thin films from MgO substrates on to glass substrates. The transferred PZT thin films exhibit single crystal structure with ferroelectric properties similar to the as-grown epitaxial films. The transferring process comprises coating of Cr-metallized surface of epitaxial PZT thin films, pressing and cementing the Cr-metallized surface on to the glass substrates by silicone rubber, and removing the MgO substrates by chemical etching. This process realizes a fabrication of high-temperature processed PZT thin films onto the glass at room temperature. The process is also available for the transformation of PZT thin films on organic film sheet. The present transfer process reduces the effects of the inevitable strain and/or constraint to rigid substrates for heteroepitaxial growth and has a potential for integration of single crystal piezoelectric PZT devices onto a wide variety of MEMS.