Characterization of Pb(Zr,Ti)O3 thin films obtained by MOD

Pb(Zr, Ti)O₃ thin films were deposited by dip-coating on polycrystalline alumina substrates by using an MOD method. The thickness and homogeneity of the films were measured as a function of dip rates and solution concentration. Heating and cooling schedules determined the main structure of the crystallized films. Rheology measurements and Fourier transform-infrared spectra were carried out to obtain a better knowledge of the solution features. A microstructural development study and some ferroelectric measurements were also carried out.     

Effects of excess Pb on structural and electrical properties of Pb(Zr0.48Ti0.52)O3 thin films using MOD process

Pb(Zr_0.48Ti_0.52)O₃ thin films at 20% excess Pb were synthesized on Pt/Ti/SiO₂/Si(100) substrates at different annealing temperatures by a metal-organic decomposition process. The microstructure of the PZT films was investigated by x-ray diffraction and atomic force microscopy. The composition of the films was characterized by Rutherford Backscattering Spectroscopy (RBS). These results showed that The PZT films have perovskite phase coexisted with PbO₂ phase. The PbO₂ phase mainly was formed by excess Pb which congregate at boundaries of crystalline grains during the annealing process and may be absorbed part of oxygen ion at normal sites, thus leading to an increase of oxygen vacancies in the PZT film. PbO₂ phase and oxygen vacancies act as pinning centres, which has an effect on the ferroelectric domain switching. This eventually resulted in an increase of fatigue rate in PZT films.     

退火工艺对溶胶凝胶Pb(Zr0.52Ti0.48)O3薄膜残余应力的影响

使用溶胶凝胶法制备了Pb(Zr0.52Ti0.48)O3 铁电薄膜,分别利用原子力显微镜、X射线衍射及面探扫描技术分析了薄膜的组织结构,并运用掠入射X射线衍射法研究了不同工艺条件下制备的薄膜的残余应力.研究表明溶胶凝胶薄膜在600℃退火30min后完全晶化,组织结构均匀.不同工艺下制备的薄膜均受残余拉应力,随着退火温度及退火时间的延长,薄膜中的残余应力逐渐增大,而随着薄膜厚度的增加,残余应力先增大然后减小.     

(111)-Oriented Pb(Zr0.52Ti0.48)O3 thin film on Pt(111)/Si substrate using CoFe2O4 nano-seed layer by pulsed laser deposition

Perovskite Pb(Zr_0.52Ti_0.48)O₃ (PZT) thin film with perfect (111)-orientation was achieved on CoFe₂O₄ seeded-Pt(111)/Ti/SiO₂/Si substrate by pulsed laser deposition technique using target with limited excess Pb. Pyrochlore phase formation was suppressed on Pt by CoFe₂O₄ nano-seed layer (~7 nm), and perovskite PZT was achieved at temperature as low as 550 °C. CoFe₂O₄ seed layer that has perfect (111)-orientation acts as a promoter for perfectly (111)-orientated growth of PZT. PZT film grown at 600 °C has higher degree of crystalline orientation, lower surface roughness, and compacted microstructure in comparison to the film grown at 550 °C. The PZT film has a nano-size grain-feature structure with grain size of about 40–60 nm. Perovskite formation was also confirmed by ferroelectric measurement. The ferroelectric properties of PZT film grown at 600 °C is higher than that grown at 550 °C which could be attributed to the enhancement of the crystalline orientation, crystallinity, and microstructure of the film.     

Pulsed laser deposition of epitaxial ferroelectric Pb(Zr,Ti)O3 films on silicon substrates

We report on the epitaxial growth and electrical properties of Pb_0.52Zr_0.48TiO₃ (PZT) thin films deposited by Pulsed Laser Deposition (PLD) on SrTiO₃ (STO)-buffered Si(001). Previously to PZT growth, 40 nm-thick (La,Sr)MnO₃ (LSMO) layer was deposited to serve as electrical bottom electrode. The 200 nm-thick PZT film epitaxy was optimized by PLD on STO-buffered Si(001).The high contrast of stable artificially poled ferroelectric surfaces evidences the good ferroelectric properties of the PZT thin film. The structural as well as the physical properties of the PZT/LSMO/STO/Si(001) structure prove that very good quality layers have been obtained for films grown on silicon substrate.     

Influence of Li doping on domain wall motion in Pb(Zr0.52Ti0.48)O3 films

Li-doped PbZr_0.52Ti_0.48O₃ (PZT) films were utilized to study the effect of A-site acceptor dopants on the mobility of ferroelectric domain walls. For chemical solution-deposited PZT films 2 μm in thickness doped with 1–3 mol% Li, the low-field dielectric permittivity remained between 1200 and 1300. With increasing Li concentration, the reversible Rayleigh constants ε _init increased from 1080 for undoped PZT films to 1240 for the films doped with 3 mol% Li, while the irreversible Rayleigh parameter showed a peak value at 1 mol% Li doping.     

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.     

Phase evolution of electron-beam evaporated Pb(Zr,Ti)O3 thin films

Solid phase reactions among electron-beam deposited PbO, ZrO₂ and TiO₂ in the thin film state as distinct from those occurring in the bulk state are described under varied annealing conditions leading to growth of perovskite PZT phase. Loss of PbO by direct high temperature (700 °C) anneal led to the growth of cubic A₂B₂O_7−x pyrochlore as well as an AB₃O₇ phase of monoclinic structure. A lower temperature initial anneal at 600 °C in O₂ ambient minimises PbO loss through phase transformation to tetragonal Pb₃O₄ and better crystallised oxide phases partially react to form pyrochlore as well as perovskite PZT. This partial reaction is kinetically driven as it goes to completion in ∼4 h resulting in transformation of pyrochlore to perovskite phase. At high temperature (800 °C) A₂B₂O_7−x phase converts to PZT perovskite and the AB₃O₇ dissociate to yield TiO₂ secondary phase inclusion in the PZT film.     

激光脉冲外延生长Pb(Zr0.52Ti0.48)O3薄膜及其特性研究

利用激光脉冲法在LaAlO3衬底上沉积制备LaNiO3薄膜作为底电极并外延生长(100) Pb(Zr0.52Ti0.48)O3铁电薄膜,系统研究了生长温度对PZT外延结构和电学特性的影响.研究发现当生长温度高于550℃时即可得到外延(100)PZT薄膜.在对所制备的PZT薄膜的结构和性能测试表明,650℃下生长的PZT薄膜外延性最佳,并且表现出优异的介电和铁电性能,介电常数ε、剩余极化Pr和矫顽场Ec分别为900、26.5 μC/cm2和52.1kV/cm.试验还证实这种外延PZT薄膜具有优良的抗疲劳特性,可用于铁电存储器的制备中去.     

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.     

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.     

Pb(Zr0.52Ti0.48)O3 nanotubes synthesis and infrared absorption properties

Herein a useful methodology to synthesize the lead zirconate titanate (PZT) nanotubes via a dip-coating deposition process with anodic aluminum oxide (AAO) template is proposed. The nano-porous AAO templates were produced using a controlled two-step electrochemical anodization technique. The PZT/AAO composite was formed using the dip-coating wetting technique. The prepared PZT precursor solution was driven into the nanopore channels of AAO template under the driving force of capillary action, subsequently the sintering process of the as-filled templates was carefully tuned to obtain Pb(Zr_0.52Ti_0.48)O₃ nanotubes of crystalline tetragonal phase with uniform pore size and ordered arrange. Fourier transform infrared spectroscopy (FTIR) results show that in the 1200–1900 cm⁻¹ band, the composite structure of PZT/AAO has obvious absorption peaks at 1471.56 cm⁻¹ and 1556.09 cm⁻¹, the absorption intensity of the composite structure is about six times of pure AAO template. The unusual optical properties found in PZT/AAO composite will stimulate further theoretical and experimental interests in ferroelectric nanostructures.     

LaNiO3缓冲层对Pb(Zr,Ti)O3铁电薄膜的影响

采用化学溶液法在Pt／Ti／SiO2／Si衬底上制备了PbZr0．4Ti0.6O3／LaNiO3(PZT／LNO)多层薄膜。X射线衍射测量表明LNO缓冲层的引入使PZT薄膜(111)择优取向度减小,(100)取向增加。原子力显微镜测量表明引入LNO缓冲层使得PZT薄膜表面更加平整、致密。在LNO缓冲层上制备的PZT薄膜具有优良的铁电特性和介电特性：LNO缓冲层厚度为40nm时,500kV／cm的外加电．场下。剩余极化(Pr)为37．6μC／cm^2,矫顽电场(Ec)为65kV／cm;100kHz时,介电常数达到822,并且发现LNO缓冲层的厚度为40nm,PZT的铁电、介电特性改进最为显著。     

Conduction at domain walls in insulating Pb(Zr0.2 Ti0.8)O3 thin films

Domain wall conduction in insulating Pb(Zr(0.2) Ti(0.8))O(3) thin films is demonstrated. The observed electrical conduction currents can be clearly differentiated from displacement currents associated with ferroelectric polarization switching. The domain wall conduction, nonlinear and highly asymmetric due to the specific local probe measurement geometry, shows thermal activation at high temperatures, and high stability over time.     

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.