Electrical properties of sputtered PZT films on stabilized platinum electrode

PZT (54/46) thin films were deposited by r.f. magnetron sputtering followed by a post-annealing treatment on silicon substrates. The crucial role of a Ti adhesion layer on the Ti/Pt bottom electrode is presented. The deposition conditions and the thickness of Ti have dominant effects on the interactions between Ti and Pt during the annealing treatment. The Pt layer, whatever its thickness, did not act as a barrier against Ti-out diffusion. The stability of the bottom electrode was achieved by using a TiO_x layer instead of a pure metallic Ti adhesion layer. The electrical properties of PZT films in terms of dielectric and ferroelectric performance were evaluated, particularly as a function of the PZT film thickness.     

Effect of electrode and substrate on the fatigue behavior of PZT thick films fabricated by aerosol deposition

10 μm-thick lead zirconate titanate (PZT) films with identical LaNiO₃ (LNO) top and bottom electrodes were fabricated on silicon and yttria-stabilized zirconia (YSZ) substrates by aerosol deposition (AD). A Pt electrode was also made for comparison. The dielectric, ferroelectric and fatigue behaviors at different fields were investigated. The PZT films on YSZ/LNO showed the highest dielectric and ferroelectric properties and good fatigue behavior under various fields. PZT films with a Pt electrode also showed good fatigue behavior up to 10⁸ cycles as thicker film can minimize the effect of defect entrapment near the interface.     

底电极原位退火与沉积温度对PZT薄膜性能影响研究

采用磁控溅射工艺,在Pt/Ti底电极上沉积锆钛酸铅(PZT)薄膜,研究了原位退火温度与底电极沉积温度对溅射PZT薄膜结晶取向、微观结构、介电性能、铁电性能及疲劳性能的影响。X射线衍射(XRD)和扫描电子显微镜(SEM)分析结果表明,随着电极沉积温度升高,Pt晶粒尺寸增大,随着退火温度升高,PZT薄膜致密性变差。对室温制备的Pt/Ti底电极进行200 ℃原位退火30 min后,易于促进PZT薄膜沿(100)择优取向,而高温制备或经高温退火处理的Pt/Ti底电极更有利于PZT薄膜的(111)晶向生长。电学性能分析表明,室温制备的Pt/Ti底电极在经200 ℃原位退火30 min后,其PZT薄膜介电性能最优,同时展现较高的剩余极化强度和最小的矫顽场强,经历10⁸次极化翻转后,初始极化下降仅为11％。     

Thermal treatment effect on the magnetoelectric properties of (Ni0.5Zn0.5)Fe2O4/Pt/Pb(Zr0.3Ti0.7)O3 heterostructured thin films

Magnetoelectric (ME) property modulation in heterostructured (Ni_0.5Zn_0.5)Fe₂O₄/Pt/Pb(Zr_0.3Ti_0.7)O₃ (NZFO/Pt/PZT) thin films on platinized Si substrate by thermal annealing condition variation was studied. In an attempt to prevent interfacial reaction between NZFO and PZT layers during high temperature annealing, thin Pt layer was deposited which can serve as inter-diffusion barrier as well as electrode. The ferroelectric, magnetic, and ME properties of the heterostructured film were noticeably modulated due to microstructural evolution and clamping relaxation developed during thermal annealing process. Room temperature ME voltage coefficient of the heterostructured thin films was enhanced with increasing annealing temperature and reached to 29 mV/cm·Oe when annealed at 650 °C.     

Preparation of ferroelectric Pb(Zr0.52 Ti0.48)O3 thin films by sol-gel processing

Ferroelectric Pb(Zr_0.52 Ti_0.48)O₃ thin films were prepared by sol-gel processing on the Pt/Ti/SiO₂/Si(100) substrates. Effects of the concentration (0.2–0.8 M) of the starting solution (Pb/Zr/Ti= 1.1/0.52/0.48) and the sintering temperature (500–700 ‡C) on crystallinity, microstructure and electrical properties of PZT thin films were investigated. For the thin film prepared at 0.4 M starting solution, the highest crystallinity appeared at a sintering temperature of 650 ‡C. The average grain size of the PZT thin films was about 0.17 Μm. The film thickness was about 0.2 Μm. The relative dielectric constant and the dissipation factor of the film measured at 1 kHz were about 750 and 4.3%, respectively. The remnant polarization (Pr) and coercive field (Ec) of the film measured at the applied voltage of 5 V were about 49 ΜC/cm² and 134 kV/cm, respectively.     

Combined XPS and TPR study of sulfur removal from a Pt/BaO/Al2O3 NO x storage reduction catalyst

Pt/Al₂O₃ and Pt/BaO/Al₂O₃ catalysts (1 wt% Pt, 10 wt%BaO) were sulfated under conditions simulating a real NSR catalyst operation. Comparative TPR and XPS studies of sulfur removal from Pt/Al₂O₃ and Pt/BaO/Al₂O₃ catalysts indicate that the sulfur removal from Al₂O₃ surface precedes reductive decomposition of BaSO₄ (250–400 °C). Barium sulfate decomposition started with further increase in desulfation temperature at the point of surface atomic ratio Ba:S = 1 (~450^o). Simultaneously, an intensive formation of sulfide species on the catalyst surface was observed. Thermodynamic analysis of the desulfation process allows us to hypothesize that barium sulfide formation may hinder sulfur removal under reducing conditions.     

Improvement of reliability and dielectric breakdown strength of Nb-doped lead zirconate titanate films via microstructure control of seed

A Pb(Zr,Ti)O₃ (PZT) seed layer without Pb-deficient defective areas was developed to improve the dielectric breakdown strength and lifetime of thin film piezoelectric actuators. The proportion of defective area in the seed layers was reduced by adjusting the amount of Pb excess in the solution, combined with implementation of a dense, large-grained (>200 nm) Pt bottom electrode. The optimal Pb excess amount in the solution was about 20 at%; seeding was improved when a slightly Ti-rich composition (relative to the morphotropic phase boundary) was utilized. It was found that the dielectric breakdown strength and lifetime of PZT films improved as the proportion of visible defective area on the PZT seed layer decreased. Dielectric breakdown strength increased from approximately 300 kV/cm to about 1 MV/cm. The lifetime, characterized by highly accelerated lifetime testing, was increased 60 times by reducing the fraction of defective area. The activation energy (E_a) and voltage acceleration factor (N) for failure of devices (eg, patterned PZT films) were 1.12 ± 0.03 eV and 4.24 ± 0.07 respectively.     

Fine-patterning of sol-gel derived PZT film by a novel lift-off process using solution-processed metal oxide as a sacrificial layer

Sub-5 µm pattern of sol-gel derived lead-zirconium-titanate (PZT) film with a thickness of 80–390 nm was successfully prepared on Pt(111)/TiO_x/SiO₂/Si (100) substrate by a novel lift-off process using solution-processed metal oxides as a sacrificial layer. The process is simply divided into three steps: In-Zn-O (IZO) sacrificial layer spin-coating and patterning, PZT film formation followed by lift-off process. The results suggested that the IZO layer is effective in preventing PZT crystallization because of its thermal stability during PZT post-annealing, and its barrier-effects between the spin-coated PZT precursor and the Pt/TiO_x substrate. Consequently, the micro-pattern of lift-off PZT exhibited better properties than that formed by wet-etching. In particular, the lift-off PZT films possessed better ferroelectric properties, higher break-down voltage, and more well-defined shape than those of films patterned by conventional wet-etching. This lift-off process shows great promise for highly integrated devices due to its fine pattern-ability.     

Film thickness dependence of the dielectric properties of SrTiO3/BaTiO3 multilayer thin films deposited by double target RF magnetron sputtering

Four-layer SrTiO₃/BaTiO₃ thin films ((ST/BT)₄) with various thicknesses deposited on Pt/Ti/SiO₂/Si substrates at 500 °C by double target RF magnetron sputtering have been investigated using X-ray diffraction (XRD), scanning electron microscopy (SEM), profilometry, capacitance-voltage and current-voltage measurements. The XRD patterns reveal the frame formation of the sputter deposited (ST/BT)₄ with controlled modulation. The adhesion between the Pt bottom electrode layer and the BT layer is excellent. The dielectric constant of the (ST/BT)₄ multilayer thin film increases with increasing film thickness. The effects of temperature, frequency, and bias voltage on the dielectric constant of the (ST/BT)₄ multilayer thin films are discussed in detail. The leakage current density of the (ST/BT)₄ multilayer with a thickness of 450.0 nm is lower than 1.0 × 10⁻⁸ A/cm² for the applied voltage of less than 5 V, showing that the multilayer thin films with such a characteristic could be applied for use in dynamic random access memory (DRAMs) capacitors.     

Hysteretic properties of Mn-doped Pb(Zr,Ti)O3 thin films

Pb(Zr,Ti)O₃ (PZT 30/70) and Mn-doped Pb(Zr,Ti)O₃ (PMZT 30/70) thin films have been fabricated on Pt/Ti/SiO₂/Si substrates by a chemical solution deposition technique. The experiments found that the addition of Mn in PZT thin films greatly improves the ferroelectric properties of thin films. It is demonstrated that the Mn-doped (1 mol%) PZT showed fatigue-free characteristics at least up to 10¹⁰ switching bipolar pulse cycles under 10 V and excellent retention properties. The Mn-doped PZT thin films also exhibited well-defined hysteresis loops with a remnant polarization (Pr) of 34 μC/cm² and a coercive field (Ec) of 100 kV/cm for the thickness of 300 nm. Dielectric constant and loss (tanδ) for Mn doped PZT thin films are 214 and 0.008, respectively. These figures compare well with or exceed the values reported previously. In this paper, the mechanism by which Mn influences on the ferroelectric properties of PZT thin films has also been discussed.     

Ferroelectric properties of PZT/BFO multilayer thin films prepared using the sol-gel method

In this study, Pb(Zr_0.52Ti_0.48)O₃/BiFeO₃ [PZT/BFO] multilayer thin films were fabricated using the spin-coating method on a Pt(200 nm)/Ti(10 nm)/SiO₂(100 nm)/p-Si(100) substrate alternately using BFO and PZT metal alkoxide solutions. The coating-and-heating procedure was repeated several times to form the multilayer thin films. All PZT/BFO multilayer thin films show a void-free, uniform grain structure without the presence of rosette structures. The relative dielectric constant and dielectric loss of the six-coated PZT/BFO [PZT/BFO-6] thin film were approximately 405 and 0.03%, respectively. As the number of coatings increased, the remanent polarization and coercive field increased. The values for the BFO-6 multilayer thin film were 41.3 C/cm² and 15.1 MV/cm, respectively. The leakage current density of the BFO-6 multilayer thin film at 5 V was 2.52 × 10^-7 A/cm².     

Electrochemically assisted photocatalytic degradation of oxalic acid on particulate TiO2 film in a batch mode plate photoreactor

Electrochemically assisted photocatalytic degradation of oxalic acid was studied in a batch mode plate photoreactor composed of particulate TiO₂ film immobilized on Ti metal plate (Ti/TiO₂ electrode) and Pt wires immersed in a flowing film of aqueous solution (Pt counter electrode). The degradation rate of oxalic acid was followed as a function of the potential of the Ti/TiO₂ electrode, the oxygen concentration and the light intensity. The presence of oxalic acid caused an increase in the measured photocurrent by one order of magnitude which is due to its reaction with photogenerated holes. The degradation rate increased with increasing potential up to 0.5 V vs SCE, then the increase was more gradual. Electrochemically assisted photocatalytic degradation of oxalic acid also proceeded in the absence of oxygen. The photogenerated electrons caused hydrogen evolution (low oxygen concentration) or predominantely oxygen reduction (high oxygen concentration) on the Pt counter electrode.     

The preparation and properties of PZT thin film by sputering method

The ferroelectric PZT thin films were prepared on Pt/Ti/SiO₂/Si substrate by RF sputtering method followed by the rapid thermal annealing. The preparation of the Pt and Ti thin films as bottom electrode, and their influences on the PZT thin films were studied in details. The substrate temperature during sputtering was room temperature; the rapid thermal annealing temperature was 500°C-750°C and the annealing time was 30-70s. The influences of different preparation parameters on the structure and electric properties were studied with X-ray diffraction technique and RT66A Standardized Ferroelectric Test System. The electric properties of the prepared PZT thin film was: P_a=39μc/cm₂, P_r = 9.3 μc/cm², E_c=28KV/mm, ε=300, p=10⁹ω⋅cm.     

Micro-patterning of PZT thick film by lift-off using ZnO as a sacrificial layer

Micro-pattern of 8.2-μm-thick PZT films was prepared on Pt/Ti/SiO₂/Si (1 0 0) substrate wafer by combining composite sol–gel and a novel lift-off using ZnO as a sacrificial layer. The processes include ZnO sacrificial layer deposition and patterning, PZT film preparation, and final lift-off. The results reveal the micro-pattern was better than that formed by wet etching, the PZT thick films patterned by lift-off possessed similar dielectric characters, better ferroelectric properties, and higher breakdown voltage than those of films patterned by wet etching. The lift-off is suitable for micro-patterning of PZT thick films.     

Bottom electrode crystallization of PZT thin films for ferroelectric capacitors

The bottom electrode crystallization (BEC) method was applied to the crystallization of PZT thin films deposited by laser ablation over Si/SiO₂/Ti(Zr)/Pt structures, with the platinum films being deposited at two different temperatures. The results were compared with those obtained by rapid annealing with halogen lamps and furnace annealing. PZT films crystallized over Pt made at lower temperature with Ti adhesion layers tend to have a (1 1 1) preferential orientation, while those deposited on platinum made at higher temperature tend to have a (1 0 0)/(1 1 1) mixed orientation. When Zr adhesion layers are used, the PZT films crystallized over Pt have a preferential (1 0 0) orientation, except for films deposited over Pt made at 500 °C and crystallized with a high heating rate. The ferroelectric properties of the films crystallized with the BEC method are good, being similar to those obtained with the other crystallization methods using the same parameters.     

Phase and Texture Evolution in Chemically Derived PZT Thin Films on Pt Substrates

The crystallization of lead zirconate titanate (PZT) thin films was evaluated on two different platinum‐coated Si substrates. One substrate consisted of a Pt coating on a Ti adhesion layer, whereas the other consisted of a Pt coating on a TiO₂ adhesion layer. The Pt deposited on TiO₂ exhibited a higher degree of preferred orientation than the Pt deposited on Ti (as measured by the Full Width at Half Maximum of the 111 peak about the sample normal). PZT thin films with a nominal Zr/Ti ratio of 52/48 were deposited on the substrates using the inverted mixing order (IMO) route. Phase and texture evolution of the thin films were monitored during crystallization using in situ X‐ray diffraction at a synchrotron source. The intensity of the Pt₃Pb phase indicated that deposition on a highly oriented Pt/TiO₂ substrate resulted in less diffusion of Pb into the substrate relative to films deposited on Pt/Ti. There was also no evidence of the pyrochlore phase influencing texture evolution. The results suggest that PZT nucleates directly on Pt, which explains the observation of a more highly oriented 111 texture of PZT on the Pt/TiO₂ substrate than on the Pt/Ti substrate.     

O2 reduction at the Pt/Nafion interface in 85% concentrated H3PO4

The kinetics of oxygen electroreduction have been studied on a smooth platinum electrode coated with Nafion® in concentrated 85% H₃PO₄. The effects of Nafion® coatings of different thickness on O₂ electroreduction at a smooth Pt rotating disk electrode with 85% phosphoric acid as the bulk electrolyte were examined. The kinetic current increases with increasing Nafion® film thickness while the diffusion limiting current decreases with increasing Nafion® film thickness. A O₂ concentration profile model for the Pt/Nafion®/bulk electrolyte has been established, and this model can be used to explain the O₂ reduction polarization results. The performance of Nafion®-modified, high surface area Pt/carbon air cathodes for use in the H₂–air concentrated phosphoric acid fuel cell was also studied.     

High Piezoelectric Longitudinal Coefficients in Sol–gel PZT Thin Film Multilayers

A five‐layer stack of lead zirconate titanate (PZT) thin films with Pt electrodes was fabricated for potential applications in nanoactuator systems. The 1 μm thick PZT films were deposited by a sol–gel technique, the platinum electrodes by sputtering. The PZT films were crack‐free, in spite of the use of silicon as a substrate, suggesting an increased toughness of the metal–ceramic composite. For piezoelectric characterization, the intermediate electrodes were liberated by successive etching of the PZT and Pt layers, obtaining a functional three‐ layer stack. A total thickness change of 5.2 nm was achieved with 10 V, measured by double beam laser interferometry. The small signal response was obtained as 0.49 nm/V. Finite element simulations were made to account for the thickness change in the substrate due to the transverse piezoelectric effect. The average response corresponds to an average d_33,f of 120 pm/V. The multiple annealed buried layers show clearly a better performance with up to 175 pm/V. It is concluded that the electrode interfaces in the interior exhibit higher qualities, as supported by transmission electron microscopy, and that the multiple anneals were beneficial for PZT thin film quality.     

Enhanced ferroelectric properties of La-substituted BiFeO3 thin films on LaSrCoO3/Pt/TiO2/SiO2/Si (1 0 0) substrates prepared by the soft chemical method

Bi_0.85La_0.15FeO₃ (BLFO015) thin films were deposited by the polymeric precursor solution on La_0.5Sr_0.5CoO₃ substrates. For comparison, the films were also deposited on Pt bottom electrode. X-ray diffraction data confirmed the substitutions of La into the Bi site with the elimination of all secondary phases under a substitution ratio x = 15% at a temperature of 500 °C for 2 h. A substantial increase in the remnant polarization (P_r) with La_0.5Sr_0.5CoO₃ bottom electrode (P_r ≈ 34 μC/cm²) after a drive voltage of 9 V was observed when compared with the same film deposited on Pt substrate. The leakage current behavior at room temperature decreased from 10^?8 (Pt) to 10^?10 A/cm² on (La_0.5Sr_0.5CoO₃) electrode under a voltage of 5 V. The fatigue resistance of the Au/BLFO015/LSCO/Pt/TiO₂/SiO₂/Si (1 0 0) capacitors with a thickness of 280 nm exhibited no degradation after 1 × 10⁸ switching cycles at a frequency of 1 MHz.     

Effects of Thermal Annealing on the Structure of Ferroelectric Thin Films

The effects of thermal annealing on the structure of polycrystalline Pb(Zr_0.3Ti_0.7)O₃ (PZT) ferroelectric thin films prepared by chemical solution deposition on Pt/TiO _x electrode stacks were studied using scanning electron microscopy, transmission electron microscopy (TEM), and grazing incidence X-ray specular and diffuse reflectivity of synchrotron radiation. The stratified multilayered structure and element diffusions in the sample were characterized by TEM. Global statistical structural parameters including the density, surface or interface roughness and thickness of each layer in the samples were obtained from fitting the X-ray specular reflectivity using a homogeneous stratified multilayer model of PZT/Pt/TiO _x /SiO₂. The results showed that the PZT surface and PZT/Pt interface roughness changed slightly during thermal annealing in oxygen at 700°C. By contrast, the density increase of the PZT ceramic and density decrease of the Pt-bottom electrode during annealing were observed. A high density value of the PZT ceramic film after the annealing was found, up to 99.8% of the theoretical value of the corresponding bulk ceramics. The density changes of the PZT and Pt layers were further confirmed by X-ray diffuse reflectivity. The influences of the annealing treatment on the density changes of the PZT and Pt layers were attributed to the further densification of the PZT ceramic and incorporation of light elements such as Zr, Ti and O from the neighboring layers into the Pt layer, respectively, as discussed in correlation with the TEM analyses.