Effect of Zr Content on Formation and Optical Properties of the Layered PbZr_xTi_(1-x)O_3 Films

PbZr_xTi_(1-x)O_3(PZT) fims are fabricated on F-doped tin oxide(FTO) substrates using chemical solutions containing PVP polymer and rapid thermal annealing processing.The dependence of the layered PZT multilayer formation and their optical properties on the Zr content x are examined.It is found that all the PZT films are crystallized and exhibit 110-preferred orientation.When x varies in the region of 0-0.8,the PZT films display lamellar structures,and a high reflection band occurs in each optical reflectance spectrum curve.Especially,those PZT fikms with Zr/Ti atomic ratio of 35/65-65/35 show clearly layered cross-sectional morphologies arranged alternatively by porous and dense PZT layers,and have a peak optical reflectivity of 70% and a band width of 45 nm.To obtain the optimal Bragg reflection performance of the PZT multilayers,the Zr content should be selected in the range of 0.35-0.65.     

Investigation on FR(LT)–FR(HT) phase transition and pyroelectric properties of pulsed laser deposited Pb(Zr0.93Ti0.07)O3 thin films

The preparation process, crystallinity and electrical properties of pulse laser deposited Pb(Zr_xTi_1−x)O₃ (PZT) thin films were investigated in this paper. PZT (x = 0.93) thin film samples deposited at different substrate temperatures were prepared. Si (1 1 0) was the substrate; Ag and YBCO were the top electrode and the bottom electrode respectively. The bottom electrode YBCO was deposited on the Si substrate by pulsed laser deposition (PLD), and then PZT was epitaxially deposited on YBCO also by PLD. After annealing, the top electrode Ag was prepared on PZT by thermal evaporation, and then the Ag/PZT/YBCO/Si structured thin films were obtained. The XRD and the analysis of their electrical characters showed that, when the substrate temperature was elevated from 600 °C to 800 °C, the crystallinity and electrical properties of PZT thin films became better and better, and the F_R(LT)–F_R(HT) phase transition of PZT (x = 0.93) thin films occurred at 62 °C. The PZT film deposited at 800 °C had the best pyroelectric properties, and when the F_R(LT)–F_R(HT) phase transition of this film occurred, the peak value of pyroelectric coefficient (p) was obtained, with a value of 1.96 × 10⁻⁶ C/(cm² K). The PZT film deposited at 800 °C had the highest remnant polarization (P_r) and the lowest coercive field (E_c), with the values of 34.3 μC/cm² and 41.7 kV/cm respectively.     

Au/PZT/BIT/p-Si异质结的制备与性能研究

采用脉冲激光沉积(PLD)工艺,制备了以Bi₄Ti₃O₁₂(BIT)为过渡阻挡层的Au/PZT/BIT/p-Si异质结.研究了BIT铁电层对Pb(Zr_0.52Ti_0.48)O₃(PZT)薄膜晶相结构、铁电及介电性能的影响,对Au/PZT/BIT/p-Si异质结的导电机制进行了讨论.氧气氛530℃淀积的PZT为多晶铁电薄膜,与直接淀积在Si基片上相比,加入BIT铁电层后PZT铁 关键词： 铁电薄膜 异质结构 脉冲激光沉积(PLD)     

Comparison of the effect of PLT and PZT buffer layers on PZT thin films for ferroelectric materials applications

In order to study the effect of different buffer layers on the Pb(Zr_0.52Ti_0.48)O₃ (PZT) thin films, 10-nm thick (Pb_0.72La_0.28)Ti_0.93O₃ (PLT) and Pb(Zr_0.52Ti_0.48)O₃ buffer layers have been deposited on the Pt(1 1 1)/Ti/SiO₂/Si substrates by pulsed laser deposition, respectively. The top buffer layers were also deposited on PZT thin films with the same thickness of the seed layers in order to enhance the fatigue characteristics of PZT thin films. We compared the results of dielectric constant, hysteresis loops and fatigue resistance characteristics. It was found that the dielectric properties of PZT thin films with PLT buffer layers were improved by comparing with PZT thin films with PZT buffer layers. The polarization characteristics of PZT thin films with PLT buffer layers were observed to be superior to those of PZT thin films using PZT buffer layers. The remanent polarization of PZT thin films showed 36.3 μC/cm² and 2.6 μC/cm² each in the case of use PLT and PZT buffer layers. For the switching polarization endurance analysis, PZT thin films with PLT buffer layers showed more excellent result than that of PZT thin films with PZT buffer layers.     

Electric and ferroelectric properties of PZT/BLT multilayer films prepared by photochemical metal-organic deposition

The electric and ferroelectric properties of lead zirconate titanate (PZT) and lanthanum-substituted bismuth titanate (BLT) multilayer films prepared using photosensitive precursors were characterized. The electric and ferroelectric properties were investigated by studying the effect of the stacking order of four ferroelectric layers of PZT or BLT in 4-PZT, PZT/2-BLT/PZT, BLT/2-PZT/BLT, and 4-BLT multilayer films. The remnant polarization values of the 4-BLT and BLT/2-PZT/BLT multilayer films were 12 and 17 μC/cm², respectively. Improved ferroelectric properties of the PZT/BLT multilayer films were obtained by using a PZT intermediate layer. The films which contained a BLT layer on the Pt substrate had improved leakage currents of approximately two orders of magnitude and enhanced fatigue resistances compared to the films with a PZT layer on the Pt substrate. These improvements are due to the reduced number of defects and space charges near the Pt electrodes. The PZT/BLT multilayer films prepared by photochemical metal-organic deposition (PMOD) possessed enhanced electric and ferroelectric properties, and allow direct patterning to fabricate micro-patterned systems without dry etching.     

Growth and characterization of (001)-oriented Pb(Zr0.52Ti0.48)O3/LaNiO3/LaAlO3 heterostructures prepared by pulsed laser deposition

Completely (001)-oriented ferroelectric Pb(Zr_0.52Ti_0.48)O₃/LaNiO₃ heterostructures on single-crystal LaAlO₃(001) substrates have been successfully grown by pulsed laser deposition. X-ray-diffraction analyses (–2 scan, scan and scan) indicate that good out-of-plane orientation and in-plane alignment have been obtained with the epitaxial relationship of PZT(001)//LNO(001)//LAO(001) and PZT001//LNO001//LAO001. Scanning electron and atomic force microscopic images reveal very smooth LNO surfaces with roughness of about 0.4–0.6 nm. Based on a microstructural study of the LNO and PZT films, a layer-by-layer growth mode for the LNO growth is proposed, while island growth is dominant for the PZT films. Secondary ion mass spectroscopy analyses show that no distinct interdiffusion can be found between the PZT and LNO layers. P–E hysteresis loop measurements of the PZT films with LNO as bottom electrodes and Au as top electrodes were carried out at an applied voltage of 5 V. The best remanent polarization P_r and coercive field E_c were found to be 28 C/cm² and 74.5 kV/cm, respectively. PACS 81.15.Fg; 68.55.Jk; 77.22.Ej; 77.84.Bw; 68.65.Ac     

Mechanical properties of sol-gel derived lead zirconate titanate thin films by nanoindentation

Lead zirconate titanate (PZT) thin films are deposited on platinized silicon substrate by sol-gel process. The crystal structure and surface morphology of PZT thin films are characterized by X-ray diffraction and atomic force microscopy. Depth-sensing nanoindentation system is used to measure mechanical characteristics of PZT thin films. X-ray diffraction analyses confirm the single-phase perovskite structures of all PZT thin films. Nanoindentation measurements reveal that the indentation modulus and hardness of PZT thin films are related with the grain size and crystalline orientation. The increases of the indentation modulus and hardness with grain size are observed, indicating the reverse Hall-Petch effect. Furthermore, the indentation modulus of (1 1 1)-oriented PZT thin film is higher than those of (1 0 0)- and random-oriented films. The consistency between experimental data and numerical results of the effective indentation moduli for fiber-textured PZT thin films using Voigt-Reuss-Hill model is obtained.     

(111)取向生长Pb(Zr0:95Ti0:05)O3纳米晶薄膜的铁电与热释电特性

" 在Pt/Ti/SiO2/Si基片上用溶胶-凝胶法与快速退火工艺制备了300 nm厚的锆钛酸铅Pb(Zr0:95Ti0:05)O3 (PZT95/5)反铁电薄膜．结果显示600~700 ℃晶化处理的钙钛矿PZT95/5薄膜具有高度(111)取向生长特性．薄膜的电性能测量采用金属-铁电-金属电容器结构．在20 V电压作用下,600~700 ℃晶化处理的PZT95/5薄膜显示出饱和电滞回线．在1 kHz下,600、650和700 ℃晶化的薄膜介电常数与损耗分别为519与0.028、677与0.029、987     

Structural,electric and pyroelectric properties of up and down graded PZT multilayers

Multi-layered structures, composed of thin films from materials with different compositions or physical properties, represents a way to obtain enhanced properties or even new functionalities. In this work, lead zirconate titanate PbZr_xTi_1-xO₃ (PZT; x = 0.20, 0.52, 0.80) multilayers were grown by pulsed laser deposition (PLD) on a single crystal strontium titanate (SrTiO₃, STO) substrate, using a strontium ruthenate (SrRuO₃, SRO) film as buffer layer for epitaxial growth, and also as back electrode.Up and down multi-layers were grown and their physical and structural properties were compared, up being the structure in which Zr concentration was varied from 20% near the STO substrate to 80% at the surface, while down is for the structure in which the Zr concentration starts with 80% near the substrate and ends with 20% at the surface. It was found that the electric and pyroelectric properties of the two graded structures are significantly different. The up structure presents electric properties that are comparable with those of single composition PZT films while the properties of the down structure are deteriorated, especially in terms of the leakage current magnitude. Pyroelectric signal could be measured only for the up structure. These differences were attributed to larger density of structural defects in the down structure compared to the up one. This is due to the different growth sequence: up structure starts with tetragonal PZT on cubic substrate (lower lattice mismatch, 1.1%) while down structure starts with rhombohedral PZT on cubic substrate (larger lattice mismatch, almost 5%).     

Highly (100) oriented Pb(Zr<Subscript>0.52</Subscript>Ti<Subscript>0.48</Subscript>)O<Subscript>3</Subscript>/LaNiO<Subscript>3</Subscript> films grown on amorphous substrates by pulsed laser deposition

Pb(Zr_0.52Ti_0.48)O₃ (PZT)/LaNiO₃ (LNO) thin films with highly (100) out of plane orientation were produced on SiO₂/Si(100) and alkaline earth aluminosilicate glass substrates by pulsed laser deposition (PLD). Orientations of both PZT and LNO films were evaluated using X-ray diffraction. The pure (100)-oriented PZT/LNO films were obtained under optimized deposition conditions. Time of flight-secondary ion mass spectrometry analysis showed that LNO could effectively block interdiffusion between the PZT films and the substrates. Fairly smooth surfaces of the PZT films with roughness of about 4 nm were observed using an atomic force microscope. Cross sectional examination revealed that the films grew in columnar grains. The PZT films grown on both SiO₂/Si and glass substrates demonstrated very good ferroelectric characteristic at room temperature with remnant polarization of up to 26 μC/cm². PACS 79.20.DS; 77.84.DY; 78.70.Ck     

多层铁电陶瓷击穿分析及优化

建立了多层串联PZT95/5爆电换能组件3维数值模型,对固化封装条件下陶瓷介质击穿问题进行了计算分析,计算结果表明:在不改动器件外部结构尺寸条件下,采用等厚度PZT95/5叠片结构布局对进一步提高输出电压方面存在瓶颈。为克服上述影响以及降低爆电换能组件击穿概率,提出了PZT95/5铁电陶瓷非等厚度布局解决方案。为实现上述设想,通过引入不等式约束条件计算得到一组非等厚度优化布局,将爆电换能组件所用PZT95/5铁电陶瓷数量减至19片,同时有效实现该布局下,各片PZT95/5陶瓷电压均低于对应厚度击穿电压的优化目标。     

Effect of Pb2Ru2O7-x (PRO) conductive interfacial layers on ferroelectric properties of Pt/Pb(Zr0.35Ti0.65)O3/Pt capacitors for nonvolatile memory applications

A conductive material, Pb₂Ru₂O_7-x (PRO), containing Pb in a cubic structure was introduced into a Pt/PZT interface in an attempt to improve the ferroelectric properties of PZT films. PRO and PZT films were prepared by rf magnetron sputtering and chemical solution deposition, respectively. The resistivity of PRO thin films in a hybrid-type electrode (PRO/Pt) structure was approximately 35–45 μΩ·cm and the surface roughness remained constant with increasing annealing temperature. The PRO interlayers suppressed the loss of Pb in PZT layers by diffusion to the Pt/PZT interface. The increase in remanent polarization was largely dependent on the PRO interlayers inserted at the bottom-Pt/PZT interface rather than at the top-Pt/PZT interface. In addition, the leakage-current behavior of PZT films in a sandwich structure was improved substantially compared to the case of PRO interlayers only at the bottom-Pt/PZT interface. Thus, the PRO interlayers play an important role in improving the ferroelectric properties of PZT thin films for use in nonvolatile memory device applications. PACS 68.55.-a; 73.40.Rw; 73.61.Ng; 77.55.+f; 81.15.Cd     

溶胶-凝胶法制备Pb(Zr1?xTix)O3复合梯度薄摸以及介电与热释电特性

"在Pt/Ti/SiO2/Si基片上用溶胶-凝胶法生长制备了PZT(Pb(Zr1-xTix)O3)复合梯度铁电薄膜． 薄膜最终结构由6层组成,"向上"梯度薄膜在Pt底电极上的第一层从PbZrO3开始,顶层是PZT(50/50),即第一层是PbZrO3,第二层PZT90/10 (10%Ti),第三层是PZT80/20,第四层PZT70/30,第五层PZT60/40,第六层PZT50/50．每一层与此相反的是"向下"梯度PZT薄膜．用X射线衍射、俄歇电子能谱和阻抗分析来研究梯度薄膜的结构与介电特性．600     

MD simulation of nanoindentation on (001) and (111) surfaces of Ag–Ni multilayers

We perform MD simulations of the nanoindentation on (001) and (111) surfaces of Ag–Ni multilayers with different modulation periods, and find that both the hardness and maximum force increase with the increase of modulation period, in agreement with the inverse Hall–Petch relation. A prismatic partial dislocation loop is observed in the Ni(111)/Ag(111) sample when the modulation period is relatively large. We also find that misfit dislocation network shows a square shape for the Ni(111)/Ag(111) interface, while a triangle shape for the Ni(001)/Ag(001) interface. The pyramidal defect zones are also observed in Ni(001)/Ag(001) sample, while the intersecting stacking faults are observed in Ni(111)/Ag(111) sample after dislocation traversing interface. The results offer insights into the nanoindentation behaviors in metallic multilayers, which should be important for clarifying strengthening mechanism in many other multilayers.     

Influences of thin Ni layer on the electrical and absorption properties of PZT thin film pyroelectric IR sensors

A solid precursor was used to prepare ferroelectric lead zirconate titanate (PZT) 30/70 thin films using the sol–gel deposition method. To apply PZT thin films for uncooled pyroelectric IR sensors, a Ni layer was deposited onto the PZT thin films, serving both as a selective absorption layer and as the top electrode. The absorption properties of such Ni coated multi-layered pyroelectric sensors were studied in the visible and infrared wavelength ranges. The maximum absorption coefficient of this type of IR sensor was measured to be 0.8 at 0.633 μm and 0.7 at 4 μm wavelength, respectively. A striking asymmetric polarization hysteresis loop in these PZT thin films with Ni as the top electrode was observed as a direct consequence. This asymmetric polarization was attributed to cause the difference in the dynamic pyroelectric responses in these Ni/PZT/Pt films, poled either positively or negatively before the measurement.     

Pulsed laser deposition of lead-zirconate-titanate thin films and multilayered heterostructures

There is an increasing interest in lead-zirconate-titanate (PZT) based ferroelectric thin film and devices in recent years. Pulsed laser deposition (PLD) technique has been demonstrated to be a versatile and successful tool for the deposition of epitaxial multi-component metal oxide films and heterostructures. This review presents a reasonable understanding of the relationship between PLD processing and composition, crystal structure and orientation of PZT ferroelectric thin films, and heterostructures. Processing-related issues from PLD of PZT thin films and material-integration strategies developed to fabrication of highly oriented or epitaxial PZT thin film based capacitors with excellent ferroelectric properties are discussed in detail. PACS 81.15.Fg; 68.55.Jk; 77.22.Ej     

Ferroelectric properties of bilayer structured Pb(Zr0.52Ti0.48)O3/SrBi2Ta2O9 (PZT/SBT) thin films on Pt/TiO2/SiO2/Si substrates

Pb(Zr_0.52Ti_0.48)O₃ (PZT) thin films with large remanent polarization and SrBi₂Ta₂O₉ (SBT) thin films with excellent fatigue-resisting characteristic have been widely studied for non-volatile random access memories, respectively. To combine these two advantages_, bilayered Pb(Zr_0.52Ti_0.48)O₃/SrBi₂Ta₂O₉ (PZT/SBT) thin films were fabricated on Pt/TiO₂/SiO₂/Si substrates by chemical solution deposition method. X-ray diffraction patterns revealed that the diffraction peaks of PZT/SBT thin films were completely composed of PZT and SBT, and no other secondary phase was observed. The electrical properties of the bilayered structure PZT/SBT films have been investigated in comparison with pure PZT and SBT films. PZT/SBT bilayered thin films showed larger remanent polarization (2P_r) of 18.37 μC/cm² than pure SBT and less polarization fatigue up to 1 × 10⁹ switching cycles than pure PZT. These results indicated that this bilayered structure of PZT/SBT is a promising material combination for ferroelectric memory applications.     

Preparation and crystallization of Pb(Zr0.95Ti0.05)O3 thin films deposited by radio-frequency magnetron sputtering with a stoichiometric ceramic target

0.95 Ti_0.05)O₃ (PZT 95/5) thin films of perovskite structure were prepared on various substrates by the radio-frequency magnetron sputtering with a stoichiometric ceramic target. The crystal structure of the films showed a strong dependency on the crystal structure of the substrates. After conventional-furnace annealing at 750 °C, crack-free and transparent epitaxial PZT 95/5 films were successfully obtained on SrTiO₃(100) substrates, and highly oriented films on LaAlO₃(012). The films on r-sapphire exhibit slightly preferred orientation along both the (040) and (122) axes of the orthorhombic PZT 95/5 phase. The films on YSZ(100) consist principally of the perovskite PZT 95/5 phase with random orientation with a small portion of unknown phase. However, the formation of the perovskite PZT 95/5 phase was not observed in the films on Si(110) or (111)Pt-coated Si substrates. The crystallization of the perovskite PZT 95/5 on these substrates could be improved by rapid thermal annealing (RTA). Single perovskite phase was obtained in the films on (111)Pt/Si which had RTA at 750 °C for 1 min. No tangible loss of Pb from the films occurred during either the sputtering or annealing. Received: 17 April 1997/Accepted: 18 November 1997     

PbZr0.4Ti0.6O3 and Ba0.9Sr0.1TiO3 reflectors derived from chemical solutions containing polymers

Ba(0.9)Sr(0.1)TiO(3) (BST)-based and PbZr(0.4)Ti(0.6)O(3)-based quasi-periodic multilayers consisting of dense and porous ferroelectric layers have been fabricated by solgel technique using chemical solutions containing polyethylene glycol (PEG) or polyvinylpyrrolidone k30 (PVP). All multilayers exhibit good performance as dielectric mirrors. For each multilayer, the maximum peak reflectivity is over 90% and the photonic stopband width is no less than 30 nm at room temperature. The reflection-band position can be easily tuned by varying the thickness of the bilayer. With the same processing conditions and number of periods, the Bragg reflection performance is almost the same for quasi-periodic PZT multilayers derived from two precursors containing different polymers. The BST multilayers deposited by using a PVP-containing precursor are superior in optical properties, including peak reflectivities and stop-band width, to those deposited by using the PEG-containing solution.     

Irradiation behavior and recovery effect of ferroelectric properties of PZT thin films

Lead zirconate titanate piezoelectric ceramics have important applications in space and aerospace technology, but the effect and physical mechanism of charged particle radiation on their performance yet to be clarified. In this study,we characterized PbZr_(0.52)Ti_(0.48)O_3(PZT) thin films, and changes in the ferroelectric properties of the films before and after electron and proton irradiation were investigated. The natural and heat treatment recoverability of the ferroelectric properties were studied, and the damages and mechanisms of different types of radiation in PZT films were also investigated.The results show that, in addition to ionization damages, electron irradiation causes certain structural damage on the PZT film, and the large structural damage caused by proton irradiation reduces drastically the ferroelectricity of the PZT film.