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.     

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.     

Preparation of (001)-oriented Pb(Zr,Ti)O3 thin films and their piezoelectric applications

Preparation of (001)-oriented Pb(Zr,Ti)O(3) (PZT) thin films and their applications to a sensor and actuators were investigated. These thin films, which have a composition close to the morphotropic phase boundary, were epitaxially grown on (100)MgO single-crystal substrates by RF magnetron sputtering. These (001)-oriented PZT thin films could be obtained on various kinds of substrates, such as glass and Si, by introducing (100)-oriented MgO buffer layers. In addition, the (001) oriented PZT thin films could be obtained on Si substrates without buffer layers by optimizing the sputtering conditions. All of these thin films showed excellent piezoelectric properties without the need for poling treatment. The PZT thin films on the MgO substrates had a high piezoelectric coefficient, d(31), of -100 pm/V, and an extremely low relative dielectric constant, epsilon(r), of 240. The PZT thin films on Si substrate had a very high d(31) of -150 pm/V and an epsilon(r) = 700. These PZT thin films were applied to an angular rate sensor with a tuning fork in a car navigation system, to a dual-stage actuator for positioning the magnetic head of a high-density hard disk drive, and to an actuator for an inkjet printer head for industrial on-demand printers.     

Preparation of (001)-oriented Pb(Zr,Ti)O/sub 3/ thin films and their piezoelectric applications

Preparation of (001)-oriented Pb(Zr,Ti)O₃ (PZT) thin films and their applications to a sensor and actuators were investigated. These thin films, which have a composition close to the morphotropic phase boundary, were epitaxially grown on (100)MgO single-crystal substrates by RF magnetron sputtering. These (001)-oriented PZT thin films could be obtained on various kinds of substrates, such as glass and Si, by introducing (100)-oriented MgO buffer layers. In addition, the (001)-oriented PZT thin films could be obtained on Si substrates without buffer layers by optimizing the sputtering conditions. All of these thin films showed excellent piezoelectric properties without the need for poling treatment. The PZT thin films on the MgO substrates had a high piezoelectric coefficient, d₃₁, of -100 pm/V, and an extremely low relative dielectric constant, epsiv_r, of 240. The PZT thin films on Si substrate had a very high d₃₁ of -150 pm/V and an epsiv_r = 700. These PZT thin films were applied to an angular rate sensor with a tuning fork in a car navigation system, to a dual-stage actuator for positioning the magnetic head of a high-density hard disk drive, and to an actuator for an inkjet printer head for industrial on-demand printers.     

Piezoelectric properties of (K,Na)NbO3 thin films deposited on (001)SrRuO3/Pt/MgO substrates

(K(x),Na(1-x))NbO(3) (KNN) thin films were deposited on (001)SrRuO(3)/(001)Pt/(001)MgO substrates by RF-magnetron sputtering, and their piezoelectric properties were investigated. The x-ray diffraction measurements indicated that the KNN thin films were epitaxially grown with the c-axis orientation in the perovskite tetragonal system. The lattice constant of the c-axis increased with increasing concentrations of potassium. The KNN thin films showed typical ferroelectric behavior; the relative dielectric constant epsilon(r) was 270 to approximately 320. The piezoelectric properties were measured from the tip displacement of the KNN/MgO unimorph cantilevers; the transverse piezoelectric coefficient epsilon*(31) (= d(31)/s(E)(11)) of KNN (x = 0) thin films was calculated to be -0.9 C/m(2). On the other hand, doping of potassium caused an increase in the piezoelectric properties, and the KNN (x = 0.16) films showed a relatively large transverse piezoelectricity of epsilon*(31) = -2.4 C/m(2).     

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。     

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.     

在金属基片上以LNO为过渡层制备Pb(Zr0.53Ti0.47)O3薄膜的电性能

采用溶胶-凝胶法和快速热处理工艺,分别以不锈钢(SS)和镍合金(NC)为基片,成功制备了表面均匀、无裂纹的锆钛酸铅(Pb(Zn0.53Ti0.47)O3,简写为PZT)薄膜.为了缓解金属基片与PZT薄膜之间由于晶格常数和热膨胀系数不同所造成的不匹配状态,引入了镍酸镧(LaNiO3,简写为LNO)薄膜作为过渡层.XRD和SEM结果表明,经过600℃下30min的晶化,PZT薄膜已经由无定型转化为钙钛矿相.以LNO为过渡层,在NC金属基片上制备的PZT薄膜具有较高的介电常数和较低的损耗(1kHz下ε=717,tanδ=0.08),较低的漏电流(50kV/cm下J=2.6×10-7A/cm2)以及较好的铁电性能(+Pr=90μC/cm2,-Pr=14 μC/cm2,Ec=32.5kV/cm).同时,在SS基片上,通过引入LNO过渡层,制备的PZT薄膜也具有比较好的性能.     

Enhanced ferroelectric properties of Pb(Zr0.80Ti0.20)O3/PbO thin films prepared by radio frequency magnetron sputtering

The Pb(Zr_0.80Ti_0.20)O₃ (PZT) thin films with and without a PbO buffer layer were deposited on the Pt(1 1 1)/Ti/SiO₂/Si(1 0 0) substrates by radio frequency (rf) magnetron sputtering method. The PbO buffer layer improves the microstructure and electrical properties of the PZT thin films. High phase purity and good microstructure of the PZT thin films with a PbO buffer layer were obtained. The effect of the PbO buffer layer on the ferroelectric properties of the PZT thin films was also investigated. The PZT thin films with a PbO buffer layer possess better ferroelectric properties with higher remnant polarization (P_r = 25.6 μC/cm²), and lower coercive field (E_c = 60.5 kV/cm) than that of the films without a PbO buffer layer (P_r = 9.4 μC/cm², E_c = 101.3 kV/cm). Enhanced ferroelectric properties of the PZT thin films with a PbO buffer layer is attributed to high phase purity and good microstructure.     

Corona poling of highly (001)/(100)-oriented lead zirconate titanate thin films

Corona poling is an interesting non-contact poling process for ferroelectric materials which, has in the past, been extensively applied to ferroelectric polymers, but not to other types of ferroelectric materials. Here, it has been investigated as an alternative technique to the conventional direct-contact poling of ferroelectric thin films.

Contact-poling and corona poling techniques were applied to highly (001)/(100) oriented lead zirconate titanate thin films of composition 52% Zr, 48% Ti (PZT52/48). Different poling voltages and durations were used to pole the samples, and the effects on the piezoelectric coefficients e_31,f and d_33,f were explored. From the magnitudes of piezoelectric coefficients and suppression of e_31,f relative to d_33,f, it was concluded that corona poling is a more suitable technique for poling PZT52/48 thin films than direct poling, since piezoelectric coefficients were higher and sample damage was less for corona poling when compared with contact-poling.     

Piezoelectric micromachined ultrasonic transducers based on PZT thin films

This paper describes fabrication and characterization results of piezoelectric micromachined ultrasonic transducers (pMUTs) based on 2-microm-thick Pb(Zr0.53Ti0.47O3) (PZT) thin films. The applied structures are circular plates held at four bridges, thus partially unclamped. A simple analytical model for the fully clamped structure is used as a reference to optimize design parameters such as thickness relations and electrodes, and to provide approximate predictions for coupling coefficients related to previously determined thin film properties. The best coupling coefficient was achieved with a 270-microm plate and amounted to kappa2 = 5.3%. This value compares well with the calculated value based on measured small signal dielectric (epsilon = 1050) and piezoelectric (e3l,f = 15 Cm(-2)) properties of the PZT thin film at 100 kV/cm dc bias. The resonances show relatively large Q-factors, which can be partially explained by the small diameters as compared to the sound wavelength in air and in the test liquid (Fluorinert 77). A transmit-receive experiment with two quasi-identical pMUTs was performed showing significant signal transmission up to a distance of 20 cm in air and 2 cm in the test liquid.     

Field-induced strain behavior for potassium sodium bismuth titanate ceramics

Data are reported for the dielectric, piezoelectric, electrostrictive, and ferroelectric properties of potassium-substituted sodium bismuth titanate, [(K(x)Na(1-x))(0.5)Bi(0.5)]TiO3. For the morphotropic phase boundary composition x = 0.2, relaxor-type behavior was observed at room temperature with piezoelectric (effective d(333) = 325 x 10(-12) m/V) and ferroelectric properties (P(R) = 25 microC/cm(2), E(C) = 30 kV/cm). A transition to a relatively frequency-independent, diffuse phase transformation region occurred with increasing temperature, with no remanent strain or coercive field. Above the transition temperature, the field-induced strain was consistent with contributions from electrostriction and field induced piezoelectricity (M(3333) = 1.9 x 10(-16) m2/V2 and d333 = 81 x 10(-12) m/V at 100 degrees C). Information is given for the temperature dependence of properties, e.g., 0.14% strain induced at 50 kV/cm at 200 degrees C. Higher potassium content x = 0.6 stabilized the ferroelectric piezoelectric region to temperatures above 200 degrees C, with a relatively stable d(333) = 150-145 x 10-12 m/V between 25 degrees C and 200 degrees C. Pb-free KNBT ceramics appear competitive with PZT, especially for higher temperature electromechanical applications.     

PZT铁电薄、厚膜及其制备技术研究进展

铁电薄、厚膜材料具有良好的铁电、压电、热释电、电光及非线性光学特性,在微电子学、光电子学、集成光学和微电子机械系统等领域有许多重要的应用.近年来,随着铁电薄、厚膜制备技术的发展,PZT厚膜材料及厚膜器件成为科学工作者研究的热点.介绍了PZT铁电薄、厚膜材料与器件的研究进展以及PZT铁电薄、厚膜制备技术及几种典型的PZT铁电薄、厚膜材料制备技术的特点,并指出了目前存在的一些问题和未来的发展方向.     

Large electrocaloric effect of highly (100)-oriented 0.68PbMg1/3Nb2/3O3-0.32PbTiO3 thin films with a Pb(Zr0.3Ti0.7)O3/PbOx buffer layer

0.68PbMg_1/3Nb_2/3O₃-0.32PbTiO₃ (PMN-PT) thin films with a lead zirconate titanate Pb(Zr_0.3Ti_0.7)O₃ (PZT)/PbO_x buffer layer were deposited on Pt/TiO₂/SiO₂/Si substrates by radio frequency magnetron sputtering technique, and pure perovskite crystalline phase with highly (100)-preferred orientation was formed in the ferroelectric films. We found that the highly (100)-oriented thin films possess not only excellent dielectric and ferroelectric properties but also a large electrocaloric effect (13.4 K at 15 V, i.e., 0.89 K/V) which is attributed to the large electric field-induced polarization and entropy change during the ferroelectric-paraelectric phase transition. The experimental results indicate that the use of PZT/PbO_x buffer layer can induce the crystal orientation and phase purity of the PMN-PT thin films, and consequently enhance their electrical properties.     

PZT铁电薄膜Sol-Gel技术制备和电性能研究

以乙酸铅(Pb(CH₃COO)₂·3H₂O)、钛酸四丁酯(Ti(OC₄H₉)₄)、硝酸锆(Zr(NO₃)₄·5H₂O)替代锆醇盐为原料,通过在Pt/Ti/SiO₂/si基片与PZT薄膜之间引入PT种子层,采用改进的sol-gel工艺制备出无裂纹,致密性好,晶粒尺寸小且分布均匀的单一钙钛矿结构的Pb(Zr_0.53Ti_0.47)O₃铁电薄膜.实验结果表明,具有PT种子层的PZT铁电薄膜电性能较好.经600℃热处理的具有PT种子层的PZT薄膜,在1kHz测试频率下,其剩余极化强度和矫顽场分别为20μC/cm²和59kV/cm,介电常数和介电损耗分别为385和0.030.     

Compositionally graded Pb(Zr,Ti)O3 thin films with different crystallographic orientations

Compositionally graded ferroelectric PbZr_xTi_1−xO₃ (PZT) films were deposited using a sputtering method and crystallized in situ at 500 °C. The films showed purely (100) or (111) crystallographic orientation when grown on Si/SiO₂/TiO₂/Pt substrates, while they exhibited c-axis epitaxial microstructure when prepared on MgO/Pt substrates. Their crystallographic orientation was controlled owing to a thin TiO_x layer sputtered on substrates prior to PZT deposition. Analysis performed by Auger depth profile clearly confirmed the variation of composition in the films. Coercive fields from 80 kV/cm to 200 kV/cm and remnant polarization as large as 45 μC/cm² were obtained. However, no typical offset was observed on hysteresis loops, unlike previous works related to graded PZT films.     

溅射工艺参数对PZT铁电薄膜相变过程的影响

采用射频磁控溅射工艺,在（１１１）Ｐｔ／Ｔｉ／ＳｉＯ２／Ｓｉ衬底上用ＰＺＴ（５３／４７）陶瓷靶制备铁电薄膜。用快速光热退火炉对原位沉积的薄膜进行ＲＴＡ处理。     

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.     

Crystallization behavior and domain structure in textured Pb(Zr0.52Ti0.48)O3 thin films by different annealing processes

Amorphous Pb(Zr_0.52Ti_0.48)O₃ (PZT) thin films were prepared on the Pt/Ti/SiO₂/Si substrates by radio-frequency magnetron sputtering at room temperature. After rapid thermal annealing (RTA) and conventional furnace annealing (CFA) at different temperatures, the films were transformed into polycrystalline PZT thin films with (111) and (100) orientation, respectively. The phase formation and ferroelectric domains correlated with different orientation were systematically investigated by X-ray diffraction and piezoresponse force microscopy. The results showed that the perovskite PZT crystal with [111] orientation hetero-nucleated preferentially on top of the PtPb intermetallic phase at the PZT/Pt interface during RTA process. It is of interest to find that the domain self-organized into a structure with rounded shape at the early stage of crystallization. While the nucleation of the films treated by CFA dominantly homo-nucleated, thus the (100) orientation grains with minimum surface energy were easy to grow. The texture effects on ferroelectric properties of PZT films were also discussed in relation to the domain structure.     

Microstructure and electrical properties of Pb(Zr0.52Ti0.48)O3 ferroelectric films on different bottom electrodes

The crystalline quality, dielectric and ferroelectricity of the Pb(Zr_0.52Ti_0.48)O₃ (PZT) films deposited on the LaNiO₃ (LNO), LNO/Pt and Pt bottom electrodes were comparatively analyzed to investigate the possibility for their application. LNO thin films were successfully prepared on Si (100) and Pt(111)/Ti/SiO₂/Si substrates by modified metallorganic decomposition (MOD). The PZT thin films were spin-coated onto the LNO, LNO/Pt and Pt bottom electrodes by sol–gel method. The crystallographic orientation and the microstructure of the resulting LNO films and PZT thin films on the different bottom electrodes were characterized by X-ray diffraction analysis. The dielectric and ferroelectric properties of PZT films on the different bottom electrodes are discussed. The PZT films deposited onto Pt/Ti/SiO₂/Si and LNO/Si substrates show strong (110) and (100) preferred orientation, respectively, while the films deposited onto LNO/Pt/Ti/SiO₂/Si substrates show the peaks of mixed orientations. PZT films on LNO and LNO/Pt bottom electrodes have larger dielectric constant and remnant polarizations compared with those grown on the Pt electrode.