Improvement electrical properties of sol–gel derived lead zirconate titanate thick films for ultrasonic transducer application

In this work, a fabrication process of piezoelectric PZT [Pb(Zr_0.52Ti_0.48)O₃] thick films up to 60 μm deposited on silicon and aluminum substrates is reported. Crystalline spherical modified PZT powder about 300 nm in diameter was used as filler. PZT polymeric precursor produced by Chemat Inc. was used as the matrix material. Spinning films were annealed at 700 °C for one hour in the furnace in air. The thickness of the thick films was measured using a scanning electron microscope (SEM). Compared with previous piezoelectric PZT composite films, the modified piezoelectric thick films exhibit better dielectric properties. The dielectric constant is over 780 and dielectric loss is 0.04 at 1 KHz. Using a PiezoCAD model, the high frequency transducer was designed and fabricated. It showed a bandwidth of 75% at 40 MHz.     

压电微能量采集器PZT厚膜制备及其图形化研究

采用环氧树脂作为中间层的真空键合技术实现体材PZT与硅片键合,再利用机械化学抛光方法将PZT减薄到适当的厚度制备了PZT铁电厚膜,构成了SiO2/Si/SiO2/Epoxy/Ag/PZT/Cr/Cu形式的压电能量采集器悬臂梁结构。基于半导体光刻技术,通过湿法化学刻蚀和切片两种方法实现了PZT厚膜图形化问题,为基于体材PZT厚膜的高性能压电能量采集器的研制打下了良好的基础。     

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.     

Residual stress development in Pb(Zr,Ti)O3/ZrO2/SiO2 stacks for piezoelectric microactuators

The residual stress of multilayers in piezoelectric microelectromechanical systems structures influences their electromechanical properties and performance. This paper describes the development of residual stress in 1.6 μm Pb(Zr_0.52,Ti_0.48)O₃ (PZT)/0.3 μm ZrO₂/0.5 μm SiO₂ stacks for microactuator applications. The residual stresses were characterized by wafer curvature or load-deflection measurements. PZT and zirconia films were deposited on 4-in. (100) silicon wafers with 0.5 μm thick thermally grown SiO₂ by sol–gel processes. After the final film deposition, the obtained residual stress of PZT, ZrO₂, and SiO₂ were 100–150, 230–270, and − 147 MPa, respectively. The average stress in the stack was  80 MPa. These residual stresses are explained in terms of the thermal expansion mismatch between the layers and the substrate. Load-deflection measurements were conducted to evaluate localized residual stresses using released circular diaphragms. The load-deflection results were consistent with the average stress value from the wafer curvature measurements. It was found that more reasonable estimates of the stack stresses could be obtained when mid-point vertical deflection data below 6 μm were used, for diaphragms 0.8–1.375 mm in diameter.     

Fabrication and characterization of piezoelectric micromachined ultrasonic transducers with thick composite PZT films

Ferroelectric microelectromechanical systems (MEMS) has been a growing area of research in past decades, in which ferroelectric films are combined with silicon technology for a variety of applications, such as piezo-electric micromachined ultrasonic transducers (pMUTs), which represent a new approach to ultrasound detection and generation. For ultrasound-radiating applications, thicker PZT films are preferred because generative force and response speed of the diaphragm-type transducers increase with increasing film thickness. However, integration of 4- to 20-microm thick PZT films on silicon wafer, either the deposition or the patterning, is still a bottleneck in the micromachining process. This paper reports on a diaphragm-type pMUT. A composite coating technique based on chemical solution deposition and high-energy ball milled powder has been used to fabricate thick PZT films. Micromachining of the pMUTs using such thick films has been investigated. The fabricated pMUT with crack-free PZT films up to 7-microm thick was evaluated as an ultrasonic transmitter. The generated sound pressure level of up to 120 dB indicates that the fabricated pMUT has very good ultrasound-radiating performance and, therefore, can be used to compose pMUT arrays for generating ultrasound beam with high directivity in numerous applications. The pMUT arrays also have been demonstrated.     

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.     

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.     

Densification and electrical properties of solution coated lead zirconate titanate thick films

Ferroelectric Pb(Zr_0.7Ti_0.3)O₃ (PZT(70/30)) powder was prepared by a sol-gel method and PZT thick films were fabricated by the screen-printing method on the alumina substrates. A concentration of a coating solution was 0.5, 1.0 mol/L and the number of coating was repeated from 0-6. The thickness of the all PZT thick films was about 60 μm. All PZT multilayered thick films showed the XRD patterns of typical peroveskite polycrystalline structure. The relative dielectric constant of the 0.5 M coated PZT-6 (6-number of sol coatings) and 1.0 M coated PZT-6 thick films were 540 and 656.2, respectively. The dielectric loss of the 0.5 M coated PZT-6 and 1.0 M coated PZT-6 thick films were 3.2% and 2.7%, respectively.     

Preparation of Pb(Zr0.52Ti484848)O3 thin films on silicon-on-insulator substrates by excimer laser deposition combined with rapid thermal annealing

In this paper we report the fabrication of ferroelectric Pb(Zr_0.52Ti_0.48)O₃ (PZT) thin films on Si-on-Insulator (SOI) substrates with and without an electrode by pulsed excimer laser deposition combined with rapid thermal annealing. Based on the structural and interfacial characteristics analysis by X-ray diffraction (XRD), Rutherford backscattering spectroscopy (RBS), cross-sectional transmission electron microscopy (XTEM) and automatic spreading resistance measurement (ASR), the film structure and orientation were revealed to be dependent on the annealing time and annealing temperature as well as deposition temperature. From RBS spectra and XTEM observation it is shown that the PZT thin films did not interact with the top silicon layers of SOI and that the composition of the film was similar to the target. The ASR measurements showed that the electrical properties of PZT/SOI as well as PZT/Pt/SOI were abrupt, and that the electrical properties of the SOI substrates were still good after the PZT growth.     

溶胶-凝胶法制作PZT微驱动器的研究

采用溶胶-凝胶法(Sol-gel)制备了PZT压电薄膜,利用PZT的压电效应制作以PZT薄膜为驱动的V型阀微驱动器.针对微驱动器的关键结构驱动膜,探索了Si/SiO2/Ti/Au/PZT/Cr/Au多层驱动膜结构制备方法,解决了在硅基底上制备PZT薄膜的问题,同时详细探讨了硅各向异性刻蚀微驱动器的关键部件驱动腔、单向阀的工艺,解决了集成制作的V型阀微驱动器的关键工艺问题,并通过SEM照片对V型阀和多层驱动膜进行了表征.研究结果表明,采用MEMS与IC技术结合的方法成功地完成了微驱动器的研制,得到的驱动腔硅杯平坦均匀.在V型阀微驱动器整体设计中需要的硅片数目少,降低了器件的复杂性,可以满足低功耗、小型化和批量生产的要求.     

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.     

Thickness-dependent electrical properties of sol–gel derived Pb(Zr0.52Ti0.48)O3 thick films using PbTiO3 buffer layers

Pb(Zr_0.52Ti_0.48)O₃ (PZT) thick films, with thickness up to 4 μm, using PbTiO₃ (PT) buffer layers were successfully prepared on silicon-based substrates by a sol–gel method. Thermal analysis (thermogravimetric–differential thermal analysis) of PT and PZT sols were used to determine the pyrolysis and annealing temperatures. X-ray diffraction results show that the PZT/PT composite thick films possess perovskite structure and the dominant crystalline orientation changes from (100) to (110) with increasing the film thickness. Furthermore, the composite thick films exhibit thickness-dependent ferroelectric and dielectric properties, i.e., the coercive field decreases while dielectric constant increases as the thickness increases. Theoretical analysis shows that the thickness-dependent electrical properties are mainly attributed to the low dielectric constant of PT buffer layer and the relaxation of internal stress in PZT films.     

电泳沉积法制备PNN-PZT厚膜的研究

利用电泳沉积法在φ50 μm的铂金丝上制备了厚度约50 μm的0.2Pb(Ni_1/3Nb_2/3)O₃-(0.8-x)PbTiO₃-xPbZrO₃ (PNN-PZT)致密压电陶瓷厚膜. 研究了不同聚合度的分散剂聚乙二醇(PEG)对悬浮液的Zeta电势和厚膜表面形貌的影响.结果显示, 加入高聚合度的分散剂PEG10000所制得的悬浮液比加入低聚合度的分散剂PEG6000制得的悬浮液更稳定, 并且电泳沉积得到的厚膜也更加致密. 本研究解释了不同聚合度的PEG对悬浮液稳定的可能原因, 并比较了连续电泳沉积法与分步电泳沉积法对厚膜表面形貌的影响, 结果表明采用分步电泳沉积法制备的厚膜更加致密. 研究了不同的烧结温度对PNN-PZT厚膜形貌和介电性能的影响, 结果显示烧结温度为1180℃时, 厚膜的介电性能最好, 介电常数达988, 介电损耗为3.7%. 测试了1180℃烧结的PNN-PZT厚膜的电压位移曲线和电滞回线, 结果表明厚膜的有效压电常数为90 pm/V,剩余极化为6.00 kV/cm.     

Deflection of wafers and cantilevers with Pt/LNO/PZT/LNO/Pt/Ti/SiO2 multilayered structure

The present paper describes a Pt/LNO/PZT/LNO/Pt/Ti/SiO₂ multilayers deposited on 4-inch Si wafers. We have evaluated the variation of the deflection of the Si wafers with deposition of each of the thin films. The deposition of the multilayers has resulted in downward deflection (center is higher than edge) of the Si wafers. The multilayers have been also deposited onto SOI wafers and fabricated into piezoelectric micro cantilevers through MEMS bulk micromachining. The micro cantilevers have shown the upward deflection. We have characterized the ferroelectric and piezoelectric properties of the PZT thin films through electrical tests of the micro cantilevers. The dielectric constant, saturation polarization, remanent polarization and coercive field were measured to be 1050, 31.3 μC/cm², 9.1 μC/cm² and 21 kV/cm, respectively. The transverse piezoelectric constant, d₃₁, was measured to be − 110 pm/V from the DC response of the micro cantilevers.     

锆钛酸铅(PZT)薄膜的自发极化与压电响应

用溶胶－凝胶法在Ｐｔ／Ｔｉ／ＳｉＯ２／Ｓｉ（１００）基片上制备了近等原子比的压电ＰＺＴ薄膜,在准同型相界附近的ＰＺＴ薄膜的应变机制是受极化控制的压电效应,内电场导致薄膜的自发极化定向,使薄膜未经极化就具有明显的压电响应。     

Synthesis and electrical properties of Pb(Zr0.52Ti0.48)O3 thick films embedded with ZnO nanoneedles prepared by the hybrid sol–gel method

Pb(Zr_0.52Ti_0.48)O₃ thick films embedded with ZnO nanoneedles (PZT–ZnO_n) were successfully prepared on Pt/Cr/SiO₂/Si substrates by the hybrid sol–gel method via spin-coating ZnO_n suspension and lead zirconate titanate (PZT) sol. To control the orientation of the films, a PbTiO₃ (PT) layer was first deposited as a seed layer. Effects of annealing method and ZnO_n contents on the corresponding orientation and crystallization of PZT–ZnO_n films were investigated by XRD and SEM. The results show that all the PZT–ZnO_n composite thick films have pure perovskite structure and high-quality film surface. The dielectric and ferroelectric properties of the PZT–ZnO_n films are close to the PZT films, and have a little decrease with the increasing of the ZnO_n contents.     

Electrical properties and chemical compatibility of PZT thick film on Ni substrates

The characteristics of Pb(Zr,Ti)O₃(PZT) thick films that were printed and fired on Ni substrates were studied. The dielectric characteristics of samples sintered at 850°C on Ni substrates could not be measured due to the formation of a NiO layer at the Ni/PZT interface. The scanning electron microscope and energy dispersive X-ray analysis of cross-sections of the PZT thick films on Ni substrates, and of a mixture of PZT and NiO powders, fired at 850°C, did not indicate the formation of secondary phases. However, the transmission electron microscopy showed around 8% solid solubility of NiO in the PZT. A new structure with a prefired, Au thick-film layer was designed in order to prevent the diffusion of the NiO to the PZT layer during sintering. The dielectric properties of the PZT layers printed and fired on the Ni substrates with the prefired Au electrode were significantly better than those of the layers on the uncoated substrate, the dielectric losses decreased from 0.23 to 0.05.     

Deposition of BaTiO3 thin films by plasma MOCVD

Barium titanium trioxide (BaTiO₃) thin films were deposited on fused silica or silicon wafer substrate from barium dipivaloylmethanate (II) (Ba(dpm)₂) and titanium tetraisopropoxide (IV) (TTIP) used as precursors in an oxygen microwave plasma. The substrates were dielectrically heated and the substrate temperatures were around 900 K during the film deposition. The deposition was performed for 15 min and the deposits were identified as BaTiO₃ by means of X-ray diffraction, X-ray photoelectron spectroscopy, infrared spectroscopy, and ellipsometry. Oxygen and barium atoms and TiO and CO molecules were identified in the plasma. These species would produce higher deposition rates at lower substrate temperatures than those did in the usual thermal metalorganic chemical vapor deposition (MOCVD). The dielectric constant of the BaTiO₃ thin film that was directly deposited on the silicon wafer substrate was as low as 10¹ order of magnitude. Because the deposit reacted with the substrate and an interdiffusional layer was formed, the platinum layer was coated on the silicon wafer substrate in order to prevent the formation of an interdiffusional layer. The dielectric constant then increased to 10³ order of magnitude.     

采用防Footing效应工艺加工的SOI微加速度计

为了解决深刻蚀绝缘体上硅(silicon on insulator,SOI)材料时存在的横向刻蚀(Footing)效应,在背腔释放SOI微机电系统(micro electro mechanical system,MEMS)工艺基础上,提出并实现了一种改进的利用背面保护电极抑制Footing效应的工艺方案.在SOI圆片上生长SiO2和Si3N4掩模材料并图形化后,背面腐蚀支撑层Si至掩埋层SiO2.去除掩埋层SiO2后,完成正面Al电极和背面保护Al电极的溅射.深反应离子干法刻蚀SOI圆片形成结构,再腐蚀背面Al薄膜完成结构释放.基于该工艺,对结构层厚度为80μm的采用双端固支梁的SOI微加速度计的结构进行设计与仿真、器件加工和最终的性能测试.加速度计在±1 g(g=9.8 m/s2)范围内的灵敏度和非线性度分别为106.7 mV/g和0.1%.实验结果表明,该改进工艺方案可以有效抑制Footing效应对器件结构的损伤,提高加工的可靠性.     

Comparative measurements of piezoelectric coefficient of PZT films by Berlincourt, interferometer, and vibrometer methods

Chemical solution deposition (CSD) techniques were used to prepare lead zirconate (Zr) titanate (Ti) (PZT) thin films with Zr/Ti ratios of 30/70 and 52/48. Usually CSD processing is restricted to making crack-free, single-layer films of 70-nm thick, but modifications to the sol-gel process have permitted the fabrication of dense, crack-free, single layers up to 200 to 300 nm thick, which can be built-up into layers up to 3-microm thick. Thicker PZT films (> 2-microm single layer) can be produced by using a composite sol-gel/ceramic process. Knowledge of the electroactive properties of these materials is essential for modeling and design of novel micro-electromechanical systems (MEMS) devices, but accurate measurement of these properties is by no means straightforward. A novel, double-beam, common-path laser interferometer has been developed to measure the longitudinal (d33) piezoelectric coefficient in films; the results were compared with the values obtained by Berlin-court and laser scanning vibrometer methods. It was found that, for thin-film samples, the d(33,f) values obtained from the Berlincourt method are usually larger: than those obtained from the interferometer and the vibrometer methods; the reasons for this are discussed.