Nanostructured heterophase thin films of lead zirconate titanate

The results of a comprehensive study of electrophysical and photoelectric properties of capacitor structures are analyzed within the proposed model of Pb(ZrTi)O₃ (PZT) films with an excess lead content, which is based on the presence of heterophase intergrain boundaries. It is shown that aging of thin-film capacitor structures is accompanied by a significant increase in the oxygen content in submicron PZT films, as well as by the modification of elemental and phase compositions of the interfaces. It is confirmed experimentally that a decrease in the switching charge in the aged PZT films is due to the oxygen sorption at heterophase crystallite boundaries containing lead oxide and to pinning of the polarization in regions adjacent to the charged boundaries. It is demonstrated that the current-voltage characteristics of the capacitor structures are described in terms of the mechanisms of space-charge-limited currents.     

Structure evolution and stoichiometry control of Pb(Zr, Ti)O3 thick films fabricated by electrospray assisted vapour deposition

Well-crystallized and stoichiometric Pb(Zr, Ti)O₃ (PZT) films, typically ∼5 μm thick, with pure perovskite-type rhombohedral structures have been successfully prepared via an electrospray assisted vapour deposition (ESAVD) method. Control of the deposition temperature within a narrow range of 300-400 °C resulted in films with the most desirable phases. PZT films with close stoichiometric match with the expected composition ratio and uniform element distribution were obtained by adding the appropriate levels of excess Pb in the precursor solutions. The annealed films were uniform, dense, compact and adherent to the substrates. The dielectric constant, ?_r, and loss tangent, tan δ, of the fabricated PZT films measured at 10 kHz were 442 and 0.09, respectively. The ESAVD deposited PZT films showed a remanent polarization, P_r, of 15.3 μC/cm² and coercive field, E_c, of 86.7 kV/cm. These results demonstrate the clear potential of the ESAVD method as a promising technique for the fabrication of thick PZT films.     

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.     

Smectic islands in antiferroelectric nanofilms

Heterochiral islands, in which topological dipoles are oppositely directed, are observed in freestanding antiferroelectric (SmC _A ^*) films. The topological dipoles in films with a transverse electric polarization and a planar molecule orientation at island boundaries are coplanar with an electric field. The topological dipoles in films with a longitudinal polarization and a planar orientation at island boundaries are perpendicular to an electric field. For a radial director orientation at island boundaries, the topological dipoles in films with a longitudinal polarization are coplanar with a field. Changing the orientation of an electric field, we can control the position of a topological defect at an island boundary and the orientation of a topological dipole. Heterochiral islands can form dimers with an anomalously small interisland distance.     

Influence of plasma pressure on the growth characteristics and ferroelectric properties of sputter-deposited PZT thin films

PZT thin films of thickness (320-1040) nm were synthesized on Si/SiO₂/Ti/Pt multilayered substrates by radio frequency magnetron sputtering. The influence of plasma pressure in the range of (0.24-4.9) Pa, during deposition, on the structural, electrical and ferroelectric properties of the PZT films was systematically studied. X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM) and cross-sectional transmission electron microscopy (XTEM) were employed for structural study. Nano-probe Energy Dispersive (EDX) line scanning was employed to investigate the elemental distribution across the film-bottom electrode interface. I-V characteristics and polarization-electric field (P-E) hysteresis loop of the films were measured. The study reveals that the plasma pressure has a strong influence on the evolution and texture of the ferroelectric perovskite phase and microstructure of the films. At an optimum plasma pressure of 4.1 Pa, PZT films are grown with 93% perovskite phase with (1 1 1) preferred orientation and uniform granular microstructure. These films show a saturation polarization of 67 μC/cm², remnant polarization of 30 μC/cm² and coercive field of 28 kV/cm which, according to the literature, seem to be suitable for device applications.Transmission electron microscopy (TEM) study shows that at a plasma pressure of 4.1 Pa, the PZT/bottom Pt interface is sharp and no amorphous interlayer is formed at the interface. At a higher plasma pressure of 4.9 Pa, poor I-V and P-E hysteresis loop are observed which are interpreted as due to an amorphous interlayer at the film-bottom electrode interface which is possibly enriched in Pb, Zr, O and Pt.     

Structural and electrical properties of polycrystalline PbZr0.5Ti0.5O3 films deposited on La0.5Sr0.5CoO3 coated silicon by sol-gel process

La_0.5Sr_0.5CoO₃ (LSCO) films have been grown on Si (100) by a metalorganic chemical liquid deposition (MOCLD) technique using lanthanum acetate, strontium acetate and cobalt acetate as the starting materials. Subsequent PbZr_0.5Ti_0.5O₃ (PZT) films were deposited onto LSCO films by a modified sol-gel method. Field-emission scanning electron microscopy and X-ray diffraction analysis show that PZT and LSCO films are polycrystalline and entirely perovskite phase. At an applied electric field of 250 kV/cm, the Pt/PZT/LSCO capacitor shows no polarization fatigue after 3×10⁹ switching cycles and an internal electric field; the remnant polarization P_r and the coercive field E_c are about 22 μC/cm² and 73 kV/cm, respectively. The dielectric constant of PZT films is 650 at a frequency of 1 kHz. Received: 20 February 2001 / Accepted: 6 June 2001 / Published online: 30 August 2001     

Proton-irradiated Pb(Zr0.52Ti0.48)O3 thick films for flexible non-volatile memory applications

We investigated the ferroelectricity in proton-irradiated flexible Pb(Zr_0.52Ti_0.48)O₃ (PZT) thick films and their non-volatile memory characteristics. The Ni-Cr metal foil substrate allowed high-quality polycrystalline PZT films with flexible functionality to be fabricated using conventional sol-gel and high-temperature annealing methods. The 10-MeV proton-irradiated PZT film exhibited an almost square polarization?electric field hysteresis curve with saturated (P_s) and remnant (P_r) polarizations of 18.9 and 17.0 μC/cm², respectively; which are slightly lower than as-grown PZT with P_s = 28.7 μC/cm² and P_r = 24.3 μC/cm². The P_r did not decrease even after 1000 cycles of continuous bending and unbending at a bending radius of 2.14 mm and decreased slightly to ～80% of its initial value after 10⁵ s. Although the P_r decreased to ～55% after 10¹⁰ cycles, the electric polarization remained switchable under positive and negative electric fields. These characteristics suggest that the flexible PZT films could be utilized in non-volatile memory device applications in environments with high doses of proton irradiation, such as those in aeronautics and nuclear power plants.     

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.     

外加电场对铁电薄膜相变的影响

采用热力学非线性理论,研究了外加电场对立方基底Pb(Zr_0.3Ti_0.7)O₃(PZT)铁电薄膜相变的影响.通过数值计算,得到了"失配应变-外加电场"相图,及外加电场与极化强度的关系.当外加电场达到186 kV/cm时,能使生长在SrTiO₃ 基底上PZT铁电薄膜从单斜r相转变为c相.在实验上,采用扫描探针显微镜通过对PZT薄膜施加不同的极化电场来研究了它的电畴翻转.从得到的压电响应相图可以看出,绝大多数的电畴是清晰可 关键词： 铁电薄膜 相变 扫描探针显微镜 失配应变     

Phase evolution and effect of pre-heating temperature on the characteristics of PZT thin films grown by using a triol sol--gel route

Lead zirconate titanate (PZT) films were fabricated on Pt(111)/Ti/SiO₂/Si(100) using the triol sol--gel method. The effect of the pre-heating temperature on the phase transformations, microstructures, electrical properties and ferroelectric properties of the PZT thin films was investigated. Randomly-oriented PZT thin films pre-heated at 400°C for 10?min and annealed at 600°C for 30?min showed well-defined ferroelectric hysteresis loops with a remanent polarization of 26.57?µC?cm^?2 and a coercive field of 115.42?kV?cm^?1. The dielectric constant and dielectric loss of the PZT films were 621 and 0.0395, respectively. The microstructures of the thin films are dense, crack-free and homogeneous with fine grains about 15–20?nm in size.     

Study of the magnetic interaction in nanocrystalline Pr-Fe-Co-Nb-B permanent magnets

The magnetic properties of an isotropic, epoxy resin bonded magnets made from Pr-Fe-Co-Nb-B powder were investigated. The magnetization reversal process and magnetic parameters were examined by measurements of the initial magnetization curve, major and minor hysteresis loops and sets of recoil curves. From the initial magnetization curve and the field dependencies of the reversible and irreversible magnetization components derived from the recoil loops it was found that the magnetization reversal process is the combination of the nucleation of reversed domains and pinning of domain walls at the grain boundaries and the reversible rotation of magnetization vector in single domain grains. The interactions between grains were studied by means of δM plots. The nonlinear behavior of δM curve approve that the short range intergrain exchange coupling interactions are dominant in a field up to the sample coercivity.The interaction domains and fine magnetic structure were revealed as the evidence of exchange coupling between soft α-Fe and hard magnetic Nd₂Fe₁₄B grains.     

Dislocation nucleation at amorphous intergrain boundaries in deformed nanoceramics

A theoretical model is proposed for lattice dislocation nucleation in deformed nanocrystalline ceramics with amorphous intergrain boundaries. According to the model, a lattice dislocation dipole nucleates at an amorphous intergrain boundary through a local plastic shear along the boundary cross section. The energy parameters of this nucleation process are calculated. It is demonstrated that the dislocation nucleation at amorphous intergrain boundaries is energetically favorable and can occur as an athermic process (without energy barrier) in the nanocrystalline phase of cubic silicon carbide 3C-SiC and in the TiN/a-Si₃N₄ nanocomposite over wide ranges of structural parameters and mechanical loads.     

Thin-film capacitor M/Pb(ZrTi)O3/M as a polarization-sensitive photocell

A steady-state short-circuit photocurrent of preliminarily polarized submicron capacitors with a polycrystalline Pb(ZrTi)O₃ (PZT) film is investigated under irradiation by light with a wavelength λ > 0.4 μm. The structures with different M/PZT interfaces that differ in the leakage current by more than an order of magnitude are found to demonstrate virtually the same value of the photocurrent, which is always directed opposite to the ferroelectric polarization of the PZT film. Although the magnitude of photocurrent is determined by the degree of polarization of the film, the observed photocurrent is not a depolarization current of the ferroelectric film. Therefore, the M/PZT/M capacitor behaves like a polarization-sensitive photocell. Within the proposed theory of a heterophase medium, the dependence of the photocurrent on the magnitude of the preliminary polarization is calculated and proves to be in reasonable agreement with the experimental results.

     

Dielectric and electromechanical properties of (1−x)PMN-xPZT ferroelectric ceramics

The dielectric and electromechanical characteristics of the (1?x)PMN-xPZT ferroelectric ceramics have been obtained at different temperatures, amplitudes, and frequencies of the measuring field and at different bias field strengths. It is shown that this ferroelectric ceramics at low and infralow frequencies possesses pronounced relaxor properties in a certain temperature range and ferroelectric properties in other temperature range. The temperature and amplitude ranges have been determined, in which the permittivity ?′ either only decreases or first increases and then decreases with an increase in the measuring field amplitude E ₀. The temperature ranges of existing the phases similar to the superparaelectric phase, dipole glass phase, and ferroelectric phase are evaluated from the temperature dependences of the coercive field E _c (T) and the remanent polarization P _r (T) and also from the reverse dependences of ?* and the electromechanical characteristics. The PZT concentration in the PMN-PZT system is determined, at which the electrostrictive constant M ₁₁ is maximum. It is demonstrated that, in the neighborhood of the temperature at a maximum of ?′, the strain S ₃ is quadratic in the field E ₌; that is, S ₃=M ₁₁ E ².     

Fiber laser annealing of nanocrystalline PZT thick film prepared by aerosol deposition

Nanocrystalline PZT thick films (1 mm square and over 10 μm thick) directly deposited onto stainless-steel substrates (PZT/SUS) by aerosol deposition (AD) technique and then annealed using focused laser beam with a fiber laser to suppress thermal damage to the back sides of the PZT/SUS and substrate near the film edge and to retain the dielectric and/or ferroelectric properties of the PZT/SUS. Compared with CO₂ laser annealing, fiber laser annealing suppressed thermal damage to the substrate. Compared with PZT/SUS annealed at 600 °C using an electric furnace, PZT/SUS annealed at 600 °C using a fiber laser showed superior properties, namely, dielectric constant ? > 1200 at a frequency of 100 Hz, remanent polarization P_r > 30 μC/cm², and coercive field strength E_c < 50 kV/cm at a frequency of 10 Hz. Furthermore, the grain growth for the PZT/SUS formed by AD technique and annealed by fiber laser irradiation was occurred within the laser spot size.     

Enhanced ferroelectric property of (Pb0.95Ca0.05)(Nb0.02Zr0.80Ti0.20)O3 thin films prepared by RF magnetron sputtering

(Pb_0.95Ca_0.05)(Nb_0.02Zr_0.80Ti_0.20)O₃ [PCNZT] thin films were deposited on the Pt(1 1 1)/Ti/SiO₂/Si(1 0 0) substrates by RF magnetron sputtering with and without a LaNiO₃ [LNO] buffer layer. Ca and Nb elements in PZT films enhance the ferroelectric property, LaNiO₃ buffer layer improves the crystal quality of the PCNZT thin films. PCNZT thin films possess better ferroelectric property than that of PZT films for Ca and Nb ion substitution, moreover, PCNZT thin films with a LNO buffer layer possess (1 0 0) orientation and good ferroelectric properties with high remnant polarization (P_r = 38.1 μC/cm²), and low coercive field (E_c = 65 kV/cm), which is also better than that of PCNZT thin films without a LNO buffer layer (P_r = 27.9 μC/cm², E_c = 74 kV/cm). The result shows that enhanced ferroelectric property of PZT films can be obtained by ion substitution and buffer layer.     

The effect of stresses on self-polarization of thin ferroelectric films

The effect of stresses, appearing due to a difference between the temperature coefficients of linear expansion of a substrate and ferroelectric film, on the self-polarization is discussed using thin films of lead zirconate-titanate PbZr_xTi_1?xO₃ (PZT) of different compositions as an example. It is assumed that the nature of self-polarization is connected with internal polarizing electric fields caused by the different density of charged surface states at the ferroelectric-layer interfaces, while tensile or compressive stresses are able only to change the polarization orientation, which causes the self-polarization to increase or decrease in magnitude. The problem of improving the efficiency of PZT films in infrared radiation detectors and memory devices is considered.     

(111)择优取向的Pb(Zr0.52Ti0.48)O3铁电薄膜的制备及研究

选用不同浓度的Pb(Zr_0.52Ti_0.48)O₃溶胶，用Sol-gel法在Pt/Ti/SiO₂/Si基片上沉积一层厚度不同的Pb(Zr_0.52Ti_0.48)O₃ (PZT52)过渡层，经400℃烘烤、550℃退火等程序后，再用Sol-gel法在PZT52过渡层上沉积Pb(Zr_0.52Ti_0.48)O _{关键词： PZT铁电薄膜 择优取向 过渡层 剩余极化强度}     

Impact of domain structure restructuring on the photomagnetization of a garnet film illuminated with circularly polarized light

A photomagnetization effect is observed for a (Tm,Bi)₃(Fe,Ga)₅O₁₂ garnet film at T = 300 K due to the restructurization of its multidomain structure. Photomagnetization (ΔM) emerges under the action of circularly polarized laser radiation in the spectral range of 450–600 nm at lasing power P < 600 kW/cm² and pulse duration τ _i ～ 7ns. The dependences of ΔM are measured on the polarization of light and magnetic field, the latter being perpendicular to the surface of the film. The maximum value of ΔM is observed for the circular polarization of light without a magnetic field. Moreover, ΔM changes sign with as the circular polarization changes sign and is zero for linear polarization.     

Annealing effect of platinum-based electrodes on physical properties of PZT thin films

This study examined the crystal structure and surface morphology, including the Ti segregation mechanism on the surface due to the inter-diffusion between Pt, Ti and TiO_x as a glue layer, according to the annealing temperature and growth orientation of a Pt film. In addition, the fatigue mechanism of ferroelectric PZT thin films deposited on a Pt-based electrode was also investigated. The nano-structure, orientation mapping, and micro-morphologies of the triangular Pt hillocks were investigated by scanning electron microscopy with an electron backscatter diffraction (EBSD) function. The D–E hysteresis loop of the ferroelectric films was measured using a Sawyer–Tower circuit at 1 kHz to obtain the remanent polarization and coercive field.