Domain wall creep in epitaxial ferroelectric Pb(Zr(0.2)Ti(0.08)O(3) thin films

Ferroelectric switching and nanoscale domain dynamics were investigated using atomic force microscopy on monocrystalline Pb(Zr(0.2)Ti(0.8))O(3) thin films. Measurements of domain size versus writing time reveal a two-step domain growth mechanism, in which initial nucleation is followed by radial domain wall motion perpendicular to the polarization direction. The electric field dependence of the domain wall velocity demonstrates that domain wall motion in ferroelectric thin films is a creep process, with the critical exponent mu close to 1. The dimensionality of the films suggests that disorder is at the origin of the observed creep behavior.     

Experimental study of the built-in field in intergrain channels of thin ferroelectric Pb(Zr,Ti)O3 films

The experimentally measured dependence of the photo-emf on the remanent polarization in thin-film M/Pb(Zr,Ti)O₃(PZT)/M capacitors correlates well with the model developed by us for the intergrain photovoltaic effect for films with columnar structure of PZT grains and heterophase intergrain boundaries. In this case, the photo-emf is determined by the depolarization field generated by the uncompensated polarization charge at PZT grain boundaries. It is shown that the magnitude and orientation of the built-in field in an intergrain channel of such PZT films can be derived from measurements of the photo-emf at zero polarization with a sensitivity on the order of a few millivolts.     

Pb(Zr0.3Ti0.7)O3铁电薄膜激光感生电压效应

采用脉冲激光沉积(PLD)技术在LaSrAlTaO₃(LSATO),LaAlO₃(LAO)和SrTiO₃(STO)的单晶倾斜衬底上成功制备了Pb(Zr_0.3Ti_0.7)O₃(PZT)薄膜,在三种倾斜衬底上生长的PZT薄膜中都首次发现了LIV效应.对PZT/LSATO薄膜在a,c轴两种不同取向择优生长下的LIV效应做了研究,发现在薄膜c轴取向择优生长 关键词： 激光感生电压效应 铁电薄膜 薄膜生长取向 原子层热电堆     

Tetragonal distortion and the domain structure of thin Pb(Zr,Ti)O3/MgO(100) films

3 /MgO(100) films was studied in synchrotron X-ray scattering experiments. In the thin epitaxial films, the tetragonal distortion of the ferroelectric phase and the transition temperature were significantly reduced. In sharp contrast to the reported mixture of the a-type and the c-type domains in thicker films, the 250-Å-thick film was purely composed of the c-type domains in the tetragonal phase. We attribute the suppression of the transition to the substrate effect, which prefers the c-type domains near the interface, and reduces the tetragonal distortion to minimize the strain energy caused by the lattice mismatch. Received: 1 November 1997/Accepted: 5 January 1998     

Effect of electric-field-assisted thermal treatment on the strain and ferroelectric properties of (100)-oriented ferroelectric Pb(Zr0.52Ti0.48)O3 thin films

Ferroelectric Pb(Zr_0.52Ti_0.48)O₃ thin films were deposited on the Pt/Ti/SiO₂/Si substrate by a sol-gel method. As a direct electric field was applied on the films during thermal treatment, strain behavior and ferroelectric properties have been investigated. X-ray diffraction patterns show that great tensile strain exists nearby the interface of the 250 nm thin film while thermal treatment assisted with direct electric field can obviously relax it. The analysis of hysteresis loops indicates that the remnant polarization increases with the thermal treatment time. These results suggest that electric-field-assisted thermal treatment is an effective way to reduce films' tensile strain through the local plastic deformation in Pt layer and enhance the remnant polarization.     

Excimer laser-induced transformation in laser ablated Pb(Zr0.52Ti0.48)O3 amorphous thin films

Pb(Zr_0.52Ti_0.48)O₃ (PZT) amorphous thin films were deposited on Si substrates at room temperature and 573?K by pulsed laser deposition. The as-deposited films were subsequently annealed at various laser power densities using a KrF pulsed excimer laser irradiation to induce the phase transformation from amorphous to ferroelectric perovskite structure. Structural analysis shows the possibility of transformation from pyrochlore to perovskite transformation when irradiated above a laser power density of 1.4?MW/cm², which is in agreement with the thermal simulation. The surface quality of the PZT films deposited on 573?K is remarkably superior to that deposited at room temperature due to the enhanced thin structure and composition homogeneity. Almost all the pyrochlore phase transformed into perovskite structure after annealing at 2.8?MW/cm² for 120?s for both PZT films deposited at room temperature and 573?K, respectively. P-E hysteresis measurement of the laser-treated PZT shows relatively low remnant polarization P _r of about 1.2?μC/cm².     

Phase states and ferroelectric properties of Pb(Zr, Sn, Ti)O3 ceramic

The ferroelectric and dielectric properties of Pb_0.99[(Zr_1−x Sn_x)_1−y Ti_y]_0.98Nb_0.02O₃ ceramic of composition (I) x=0.5, y=0.04–0.12 and (II) x=0.4, y=0.06–0.09 were studied, and the T-x and E-T diagrams were constructed. When zinc is substituted for tin, the range of coexistence of the ferroelectric and antiferroelectric phases extends. The range of the nonpolar phase shrinks when the titanium content is increased.     

不同衬底上Pb(Zr0.52Ti0.48)O3择优取向铁电薄膜的制备和研究

通过MOD法在Si(100)和Pt(111)/Ti/SiO2/Si基片上制备出LaNiO3 (LNO)薄膜.再通过修正的Sol-gel法,在Pt(111)/Ti/SiO2/Si,LNO/Si(100)和LNO/Pt/Ti/SiO2/Si三种衬底上制备出具有择优取向的Pb(Zr0.52Ti0.48)O3铁电薄膜.经XRD分析表明,LNO薄膜具有(100)择优取向的类钙钛矿结构;PZT薄膜均具有钙钛矿结构,且在Pt(111)/Ti/SiO2/Si衬底上的薄膜以(110)择优取向,在LNO/Pt/Ti/SiO2/Si和LNO/Si(100)衬底上的薄膜以(100)择优取向.经场发射SEM分析和介电、铁电性能测试表明,在LNO/Si和LNO/Pt/Ti/SiO2/Si衬底上的PZT薄膜的平均粒径、介电常数以及剩余极化强度均比以Pt/Ti/SiO2/Si为衬底的薄膜大.     

Morphology and microstructure of all-epitaxial ferroelectric tri-layered (Bi,La)4Ti3O12/Pb(Zr0.4Ti0.6)O3/ (Bi,La)4Ti3O12 thin films on SrTiO3(011)

The morphology and microstructure of all-epitaxial (Bi,La)₄Ti₃O₁₂/Pb(Zr_0.4Ti_0.6)O₃/(Bi,La)₄Ti₃O₁₂ (BLT/PZT/BLT) tri-layered ferroelectric films, grown on (011)-oriented SrTiO₃ (STO) substrates by pulsed laser deposition, are investigated by transmission electron microscopy (TEM). X-ray diffraction and electron diffraction patterns demonstrate that the epitaxial relationship between BLT, PZT and STO can be described as ; . Cross-sectional TEM images show that the growth rate of BLT is nearly two times that for PZT at the same growth conditions, and 90° ferroelectric domain boundaries lying on {110} planes are observed in the PZT layer. The 90° ferroelectric domains in the PZT layer extend up to 600 nm in length. Long domains penetrate into the neighboring columnar grain through the columnar grain boundary, whereas others are nucleating at the columnar grain boundaries. The roughness of the PZT/BLT interfaces appears to depend on the viewing direction, i.e., it is different for different azimuthal directions. Planar TEM investigations show that the grains in the top BLT layer have a rod-like morphology, preferentially growing along the [110]_BLT direction. The grain width is rather constant at about 90 nm, whereas the length of the grains varies from 150 to 625 nm. These morphological details point to the important role the crystal anisotropy of BLT plays for the growth and structure of the tri-layered films. PACS 81.15-z; 68.37.Lp; 77.84.-s     

Domain wall roughness in epitaxial ferroelectric PbZr0.2Ti0.8O3 thin films

The static configuration of ferroelectric domain walls was investigated using atomic force microscopy on epitaxial PbZr(0.2)Ti(0.8)O(3) thin films. Measurements of domain wall roughness reveal a power-law growth of the correlation function of relative displacements B(L) alpha L(2zeta) with zeta approximately 0.26 at short length scales L, followed by an apparent saturation at large L. In the same films, the dynamic exponent mu was found to be approximately 0.6 from independent measurements of domain wall creep. These results give an effective domain wall dimensionality of d = 2.5, in good agreement with theoretical calculations for a two-dimensional elastic interface in the presence of random-bond disorder and long-range dipolar interactions.     

Low-temperature laser processes for synthesizing (100)-textured Pb(Zr,Ti)O3 thin films on Si substrate

High-performance Pb(Zr,Ti)O₃, PZT, thin films were synthesized on Si substrates by using low-temperature laser-assisted processes, which combine pulsed laser deposition (PLD), laser lift-off (LLO) and laser-annealing (LA) processes. The PZT films were first grown on sapphire substrates at 400 °C, using Ba(Mg_1/3Ta_2/3)O₃, BMT, as seeding layer, by the PLD process, and were then transferred to Si substrates at room temperature by a LLO transferring process. Utilization of the BMT layer is of critical importance in those processes, since it acted as a nucleation layer for the synthesis of the PZT thin films on the sapphire substrates and, at the same time, served as a sacrificial layer during laser irradiation in the LLO process. After the LLO process, the surfaces of the PZT films were recovered by the LA process for removing the damage induced by the LLO process. A thin BMT (∼30 nm) layer is randomly oriented, resulting in non-textured PZT films with good ferroelectric properties, viz. P_r=20.6 μC/cm² and E_c=126 kV/cm, whereas a thick BMT (∼100 nm) layer is (100) preferentially oriented, leading to (100)-textured PZT films with markedly better ferroelectric properties, viz. P_r=34.4 μC/cm² and E_c=360 kV/cm. PACS 81.15.Fg; 77.84.-s     

Epitaxial Pb(Zr,Ti)O3 ultrathin films under open-circuit electrical boundary conditions

The temperature-versus-misfit-strain phase diagram of Pb(Zr,Ti)O3 ultrathin films under open-circuit electrical boundary conditions is simulated via the use of an effective Hamiltonian. Two novel phases, both exhibiting dipolar nanodomains and oxygen octahedral tilting, are discovered. The interplay between dipolar, antiferrodistortive, alloying, and strain degrees of freedom induces several striking features in these two phases, such as the chemical pinning of domain walls, the enhancement of oxygen octahedral tilting near the domain walls, and the existence of dipolar waves and cylindrical dipolar chiral bubbles.     

重温Pb(Zrx Ti1-x)O3铁电薄膜极化疲劳问题

具有ABO3型钙钛矿结构的Pb(ZrxTi1-xO3(PZT)展示出良好的铁电极化性能,是使用最广的铁电材料.然而,在将它应用于铁电存储时,PZT薄膜遭遇到极化疲劳问题而被SrBi2Ta2O9(SBT)等铁电体所替代,这一问题至今未能得到妥善解决.文章首先通过变温极化疲劳实验充分理解PZT极化疲劳的基本过程,然后有针对性地进行材料设计,获得基本无极化疲劳的PZT铁电薄膜.     

Photovoltaic effect in thin film of Pb(Zr,Ti)O3 evaporated on stainless steel

A dc photovoltaic effect has been observed in thin films of Pb(Zr, Ti)O₃ evaporated on stainless steel, in the absence of applied field. The spectral photovoltaic response of the film has a peak sensitivity around 4000 Å. The photovoltage exists only below the Curie temperature. The film device becomes semiconductive under illumination.     

重温Pb(ZrxTi1-x)O3铁电薄膜极化疲劳问题

具有ABO3型钙钛矿结构的Pb(ZrxTi1-x)O3 (PZT)展示出良好的铁电极化性能,是使用最广的铁电材料.然而,在将它应用于铁电存储时,PZT薄膜遭遇到极化疲劳问题而被SrBi2Ta2O9 (SBT)等铁电体所替代,这一问题至今未能得到妥善解决.文章首先通过变温极化疲劳实验充分理解PZT极化疲劳的基本过程,然后有针对性地进行材料设计,获得基本无极化疲劳的PZT铁电薄膜.     

Nanoscale imaging of ferroelectric domain and resistance switching in hybrid improper ferroelectric Ca3Ti2O7 thin films

Hybrid improper ferroelectrics have their electric polarization generated by two or more combined non-ferroelectric structural distortions such as the rotation and tilting of Ti-O octahedral in Ca₃Ti₂O₇ (CTO) family. In this work, we prepared different thickness CTO thin films on Pt substrates by pulsed laser deposition, and investigated their ferroelectric polarization reversal and the current transport properties by using the piezoresponse force microscopy and conducting atomic force microscopy, respectively. It is found that the CTO films exhibit clear ferroelectric domain switching and ferroelectric resistance switching behaviors, and the maximum resistive ratios of CTO film reaches ∼1750. These results demonstrate that hybrid improper ferroelectrics CTO films are promising materials for being employed in non-volatile memory and logic devices.     

(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(Zr0.52Ti0.48)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(Zr0.52Ti0.48)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(Zr0.52Ti0.48)O3薄膜.XRD分析表明,有PZT52过渡层的Pb(Zr0.52Ti0.48)O3薄膜具有(111)择优取向的钙钛矿结构,且随着过渡层厚度的增加,Pb(Zr0.52Ti0.48)O3薄膜的(111)择优取向程度越高.SEM分析表明,当PZT52过渡层的厚度达到14nm以上,Pb(Zr0.52Ti0.48)O3薄膜结晶程度得到明显改善,平均晶粒尺寸大大增加.介电、铁电性能测试表明,与没有过渡层的Pb(Zr0.52Ti0.48)O3薄膜相比,有PZT52过渡层的Pb(Zr0.52Ti0.48)O3薄膜具有较大的介电常数和剩余极化强度,而介电损耗则较小.     

Modification of ferroelectric hysteresis in Pb(Nb,Zr,Ti)O3 thin films induced by CO2 adsorption

We report on the modification of ferroelectric hysteresis in Pb(Nb,Zr,Ti)O₃ thin films under the adsorption of CO₂ gas. The samples were exposed to the gas in ultra high vacuum while different voltages between the top (Ag) and bottom (Pt) electrodes were applied. After dosing, the samples were heated from room temperature at 1.8 K/s, and a mass spectrometer was used to detect the desorbed molecules. The effective molecular sticking was demonstrated by the appearance of the carbon Auger peak in the surface of the sample and by the presence of CO₂ in the desorption curves. After +(−) 9.9 V were applied to the bottom electrode during dosing, we found a shift of −0.52 (+0.58) μC/cm² in the remnant polarization. These evidences suggest the existence of a depolarizing field induced by molecular adsorption at the surface of the top electrode, and contribute to highlight the potential use of ferroelectric thin films as gas sensors.     

Fatigue-free Pb(Zr0.52Ti0.48)O3 thin films on indium tin oxide coated substrates by a sol-gel process

Fatigue-free Pb(Zr_0.52Ti_0.48)O₃ (PZT) ferroelectric thin films were successfully prepared on indium tin oxide (ITO) coated glass substrates using the sol-gel method combined with a rapid thermal annealing process (RTA). The films post-annealed at a temperature of 700 °C for 2 min by RTA process formed (110)-oriented Pb(Zr_0.52Ti_0.48)O₃ thin films with pure perovskite structure, and had a good morphology as well. The good ferroelectricity of the prepared PZT films was confirmed by P–E hysteresis loop measurements. Fatigue characteristics showed stable behavior. Degradation in polarization was not found while the repeating cycles were up to 10¹¹, and a low leakage current density of 10⁻⁸ A/cm² was also obtained from the highly fatigue-resisted PZT thin films on ITO/glass substrates. Received: 19 October 1998 / Accepted: 29 March 1999 / Published online: 26 May 1999