Determination of the nanoscale dielectric properties in ferroelectric lead zirconate titanate (PZT) thin films

We report on nanoscale experiments with <100 nm lateral resolution being able to differentiate the effective dielectric polarisation P_z, deposited charge density σ, surface dielectric constant ε_surface, its voltage dependence ε_surface(U), as well as the built-in electric bias voltage U_int in ferroelectric lead zirconate titanate (PZT) thin films. This is possible by combining piezoresponse force microscopy (PFM) and pull-off force spectroscopy (PFS), both methods based on scanning force microscopy (SFM). The differentiation becomes possible since both P_z and σ contribute additively in PFS, while they are subtractive in PFM, hence allowing the two contributions to be separated. ε_surface can be quantified by means of the experimental PFS data and the calculated effective penetration depth of PFM developed in a finite element modelling. Finally, U_int and ε_surface(U) are derived by an absolute matching of the P_z values measured by PFM and PFS.Our nanoscale results obtained on PZT thin films reveal values for the above specified quantities that have the same order of magnitude as those obtained from macroscopic measurements reflecting the integral response using large electrode areas. However, we stress that the data reported here reveal physical properties deduced on the nanometer scale. Furthermore, they are recorded during one single experimental investigation, using one single set-up only.     

Stochastic ferroelectric switching of lead zirconate titanate thin films

We investigate the repolarization phenomenon in a ferroelectric film. Our ferroelectric sample was lead zirconate titanate (PZT) obtained by sol-gel synthesis and deposited by spin coating on ITO/glass substrate. A series of repolarizations were induced in the ferroelectric film by applying a triangular wave and the current peaks related to the switchings of the ferroelectric domains were acquired for statistical analyses. It is shown that the dynamics and statistics of polarization switchings are well simulated by a simple mean-field model in which a double-well, asymmetric potential is included to describe the asymmetry at the PZT-ITO interface.     

Fatigue of lead titanate and lead zirconate titanate thin films

The fatigue of lead titanate and lead zirconate titanate ferroelectric thin films, i.e., a change in the polarization as a function of the number of switching cycles in an external electric field, is investigated experimentally. The threshold numbers of switching cycles are determined to be 10¹⁰–10¹¹ for the lead titanate films and 10⁹–10¹⁰ for the lead zirconate titanate films. It is shown that a change in the temperature does not substantially affect the threshold number of switching cycles at which the switched polarization decreases drastically. However, an increase in the external field strength leads to a noticeable decrease in the threshold number of switching cycles. The process of fatigue is accompanied by an increase in the coercive field and the internal bias field. It is established that, as the number of switching cycles increases, the internal bias field changes more significantly as compared to the coercive field. The absence of a change in the phase composition in repeatedly switched samples indicates that the fatigue processes have a nonchemical nature. The anomaly observed in the frequency dependence of the permittivity in the frequency range 10⁶–10⁷ Hz due to the domain structure disappears after multiple switching cycles. This suggests that the observed fatigue phenomenon has a domain nature.     

Preparation and properties of lead titanate thin ferroelectric films

A new technique is proposed for preparing lead titanate ferroelectric films. The technique involves a solid-phase reaction in an oxygen environment between titanium and lead layers deposited on a substrate. The thicknesses of the component films being deposited are chosen based on the stoichiometric ratio in the compound to be synthesized. The composition and structure of the film obtained are checked by x-ray phase analysis. The films exhibit a dielectric hysteresis loop and a temperature dependence of the permittivity characteristic of ferroelectrics. A study has been made of the temperature and thickness dependences of the film coercive field. They also are shown to follow a pattern typical of ferroelectrics.     

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.     

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.     

Internal field and self-polarization in lead zirconate titanate thin films

It has been shown that 300-nm-thick polycrystalline films of lead zirconate titanate (PZT), the compositions of which correspond to the region of morphotropic phase boundary, undergo anomalous changes in the composition and the microstructure as the annealing temperature increases. This causes substantial variations in the dielectric and piezoelectric responses, the spontaneous polarization and the internal field value. It has been demonstrated that the self-polarization varies nonmonotonically with increasing the internal field and is characterized by a threshold effect. The role of excess lead oxide and its influence on the formation of the self-polarization and the change in the effective permittivity of the ferroelectric layer has been discussed.     

Electrical properties of highly (111)-oriented lead zirconate thin films

Antiferroelectric PbZrO₃ thin films were grown on Pt/Ti/SiO₂/Si substrates with predominant (111) orientation using a sol-gel process. The Pt/PbZrO₃/Pt film capacitor showed well-saturated hysteresis loops at an applied voltage of 5 V with remanent polarisation (P_r) and coercive electric field (E_c) values of 8.97 μC/cm² and 162 kV/cm, respectively. The leakage current density of the highly (111)-oriented PbZrO₃ film was less than 1.0×10⁻⁷ A/cm² over electric field ranges from 0 to 105 kV/cm. The conduction current depended on the voltage polarity. The PbZrO₃/Pt interface forms a Schottky barrier at electric fields from 20 to 160 kV/cm. The dielectric relaxation current behaviour of Pt/PbZrO₃/Pt capacitor obeys the well-known Curie-Von Schweidler law at electric field of 20-80 kV/cm, the currents have contributions of both dielectric relaxation current and leakage current.     

Superior electromechanical performance over PZT, in lead zinc niobate (PZN)–lead zirconium titanate (PZT) thin films

Strongly oriented thin films of lead zinc niobate (PZN)–lead zirconium titanate (PZT) with (La,Sr)CoO₃ lower electrodes were grown on MgO {001} substrates by pulsed laser deposition. The films were perovskite-dominated with strong in-plane and out-of-plane orientations. Room-temperature functional characterisation indicated that the films were ferroelectric, with dielectric constant ∼550 and loss tangent ∼0.08 at 1 kHz. The crystallographic strain, as a function of applied dc field, was monitored by in situ X-ray diffraction. The maximum electric-field-induced crystallographic strain (∼0.22%) was comparable to that observed in bulk, but at significantly greater field (∼150 kV cm^-1). The effective d₃₃ value obtained from the crystallographic strain data was around 150 pm V^-1, which is high for ferroelectric thin films 400 nm in thickness. The local polarisation-switching properties of the films were investigated using a piezo-response atomic force microscope. Domain maps for a 5×5 μm² region of material were recorded as a function of dc bias, and confirmed the ferroelectric switching behaviour. PACS 81.05.Je; 81.40.Vw; 68.37.Lp     

Nd掺杂对Bi4Ti3O12铁电薄膜的微结构和铁电性能的影响

利用溶胶-凝胶法在Pt/Ti/SiO₂/Si(100)衬底上制备了Nd掺杂Bi₄Ti₃O₁₂(Bi_4-xNd_xTi₃O₁₂, x=0.00,0.30,0.45,0.75,0.85,1.00,1.50)铁电薄膜样品.研究了Nd掺杂对Bi₄Ti₃O₁₂薄膜的微结构和铁电性能的影响.研究结果表明:Nd掺杂未改变Bi₄Ti₃O₁₂薄膜的基本晶体结构.在掺杂量x<0.45时,Nd³⁺只取代类钙钛矿层中的A位Bi³⁺.当x=0.45时,样品剩余极化强度达最大值,在270kV·cm^-1的电场下为32.7μC·cm^-2.掺杂量进一步增加时,结构无序度开始明显增大,Nd³⁺开始进入(Bi₂O₂)²⁺层,削弱其绝缘层和空间电荷库的作用,导致材料剩余极化逐渐下降.当掺杂量x达到1.50时,掺杂离子最终破坏(Bi₂O₂)²⁺层的结构,材料发生铁电-顺电相变.     

Evolution of the switching current during the accumulation of fatigue in lead titanate and lead zirconate titanate thin films

The fatigue processes caused by repeated cyclic switching of polarization in lead titanate and lead zirconate titanate thin films on silicon substrates by applying rectangular pulse and sine wave fields are investigated. Upon an increase in the cycling number, an increase in the coercive and internal bias fields is observed, along with a reduction in the switching current maximum, the switching time, and the switchable polarization. At the same time, no change in the mobility of domain boundaries is observed.     

Substrate clamping effects on irreversible domain wall dynamics in lead zirconate titanate thin films

The role of long-range strain interactions on domain wall dynamics is explored through macroscopic and local measurements of nonlinear behavior in mechanically clamped and released polycrystalline lead zirconate-titanate (PZT) films. Released films show a dramatic change in the global dielectric nonlinearity and its frequency dependence as a function of mechanical clamping. Furthermore, we observe a transition from strong clustering of the nonlinear response for the clamped case to almost uniform nonlinearity for the released film. This behavior is ascribed to increased mobility of domain walls. These results suggest the dominant role of collective strain interactions mediated by the local and global mechanical boundary conditions on the domain wall dynamics. The work presented in this Letter demonstrates that measurements on clamped films may considerably underestimate the piezoelectric coefficients and coupling constants of released structures used in microelectromechanical systems, energy harvesting systems, and microrobots.     

Influence of strontium concentration on the structural,morphological, and electrical properties of lead zirconate titanate thin films

We report the strontium-doping effect on polycrystalline lead zirconate titanate thin films. The thin films were prepared by the polymeric precursor method and their structural, morphological, and electrical properties were studied. The Pb_1-xSr_xZr_0.3Ti_0.7 (PSZT) thin films with strontium concentration x between 0.10 and 0.30 were heated at 700 °C for 2 h for the crystallization. The structural phase evolution, as a function of the Sr content, was followed using micro-Raman spectroscopy, specular reflectance Fourier transform infrared spectroscopy, and X-ray diffraction (XRD). With the addition of strontium to PSZT, the broadening of the Raman peaks increases. This broadening indicates a structural change of PSZT from the tetragonal phase to a pseudocubic phase. A higher dielectric constant value, as a consequence of the higher strontium concentration, was observed. This increase may indicate the presence of a phase transition from tetragonal to pseudocubic at room temperature, which corroborates the XRD and Raman-spectra analyses, and can lead us to suppose a possible decrease of the Curie temperature. The results for the remanent polarization and the coercive field, as a function of the strontium content, showed a possible phase transformation from ferroelectric to paraelectric. PACS 61.10.Nz; 68.37.Ps; 77.55.+f; 78.30.-j; 81.15.-z     

Fatigue of lead titanate and lead zirconate titanate thin films with various values of coercive and internal bias fields

The dependence of the residue polarization on the number of switching cycles in thin ferroelectric films with various thicknesses and on substrates differing by values of the coercive and internal bias fields was experimentally studied. A model describing the features of the fatigue effect in these films is proposed.     

Crystallographic orientation dependence of ferroelectric domain walls in antiferroelectric lead zirconate thin films

Domains of antiferroelectric PbZrO₃ have been studied. The (111) PbZrO₃ has lower field transitions due to the reduction of the angle between the ferroelectric polar axis and the applied electric field. The study of the permittivity reveals also that the (111) PbZrO₃ has a higher correlation of dipoles (|S_hf| = 0.007) due to the energy gain associated with their orientation. Therefore, the (111) crystallographic orientation is a better choice for obtaining easily switching domain. The dielectric response of the domain walls in the (100) and (111) PbZrO₃ are identical because they have the same environment (same grain size and similar defects) and interact in the same way. Only the domain wall density is higher in the (111) PbZrO₃ due to its lower crystallographic orientation factor. Different crystallographic directions have more obstacles due to the inhomogeneity of the crystallization and consequently has more nucleation site for domain walls.     

Dielectric properties of lead titanate thin films on corundum substrates

Ferroelectric films of lead titanate were synthesized on corundum (Al₂O₃) substrates. The main parameters that characterize the dielectric hysteresis, such as the spontaneous polarization, coercive force, internal bias field, and the phase-transition temperature, were determined. The dispersion of the permittivity was studied using impedance spectroscopy in wide temperature and frequency ranges. An anomaly in the frequency dependence of the complex permittivity was revealed at frequencies of the order of 10⁷ Hz.     

Electrical properties of thin lead titanate films on polycor substrates

The dielectric properties of synthesized films, including the permittivity dispersion, have been investigated. The fatigue processes in the films have been experimentally studied as a function of the number of cycles of external voltage switching. It is established that the main dielectric characteristics are partially recovered in the absence of external actions.     

A study of capacitance-voltage characteristics of lead zirconate titanate ferroelectric thin films and their usage to investigate polarization and coercive field

Capacitance-voltage (C-V) characteristics of lead zirconate titanate (PZT) thin films with a thickness of 130 nm were measured between 300 and 533 K. The transition between ferroelectric and paraelectric phases was revealed to be of second order in our case, with a Curie temperature at around 450 K. A linear relationship was found between the measured capacitance and the inverse square root of the applied voltage. It was shown that such a relationship could be fitted well by a universal expression of C/A = k(V+V(0))(-1/2) and that this expression could be derived by expanding the Landau-Devonshire free energy at an effective equilibrium position of the Ti/Zr ion in a PZT unit cell. By using the derived equations in this work, the free energy parameters for an individual material can be obtained solely from the corresponding C-V data, and the temperature dependences of both remnant polarization and coercive voltage are shown to be in quantitative agreement with the experimental data.