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.     

Barium titanate thin films prepared on MgO (100) substrates by coating-pyrolysis process

Barium titanate (BaTiO₃) thin films were prepared on MgO (100) substrates using metal naphthenate solution by a coating-pyrolysis process. Amorphous films pyrolyzed at 470‡C were crystallized to BaTiO₃ phase by heat treatment at higher temperatures. The crystallinity and alignment of the films depended on temperature and on atmosphere during heat treatment. Epitaxial BaTiO₃ film having (100)-orientation was obtained by heat treatment at 900‡C under oxygen partial pressure of 2x 10^-4 atm. The epitaxial BaTiO₃ film had a lattice constant of 0.401₆ nm and displayed a smooth surface with some pores dispersed on the surface. By heat treatment in air, amorphous BaTiO₃ film was obtained at 900‡C or below, and textured film with less strong (100) orientation was obtained at 1,200‡C and consisted of grains with diameter about 0.3 Μ.     

Growth of the ternary Pb(Mn,Nb)O3–Pb(Zr,Ti)O3 thin film with high piezoelectric coefficient on Si by RF sputtering

In this study, ternary ferroelectric 0.06Pb(Mn_1/3Nb_2/3)O₃–0.94Pb(Zr_0.48Ti_0.52)O₃ (PMN–PZT) thin film with high piezoelectric coefficient were grown on La_0.6Sr_0.4CoO₃-buffered Pt/Ti/SiO₂/Si substrate by RF magnetron sputtering method. The phase and domain structure along with the macroscopic electrical properties were obtained. Under the optimized temperature of 550°C and sputtering pressure 0.9 Pa, the PMN–PZT film owned large remnant ferroelectric polarization of 62 μC/cm². In addition, the PMN–PZT film had polydomain structures with fingerprint-type nanosized domain patterns and typical local piezoelectric response. Through piezoelectric force microscopy, the PMN–PZT thin film at nanoscale exhibited obvious domain reversal when subjected to in situ poling field. It was further found that the quasi-static piezoelectric coefficient of the PMN–PZT thin film reached 267 pC/N, which was about twice to that of the commercial PbZrO₃–PbTiO₃ (PZT) thin film. The optimized relaxor ferroelectric thin film PMN–PZT on silicon with global electrical properties shows great potential in the piezoelectric micro-electro-mechanical systems applications.     

Impact of fatigue behavior on energy storage performance in dielectric thin-film capacitors

The polarization hysteresis loops and the dynamics of domain switching in ferroelectric Pb(Zr_0.52Ti_0.48)O₃ (PZT), antiferroelectric PbZrO₃ (PZ) and relaxor-ferroelectric Pb_0.9La_0.1(Zr_0.52Ti_0.48)O₃ (PLZT) thin films deposited on Pt/Ti/SiO₂/Si substrates were investigated under various bipolar electric fields during repetitive switching cycles. Fatigue behavior was observed in PZT thin films and was accelerated at higher bipolar electric fields. Degradation of energy storage performance observed in PZ thin films corresponds to the appearance of a ferroelectric state just under a high bipolar electric field, which could be related to the nonuniform strain buildup in some regions within bulk PZ. Meanwhile, PLZT thin films demonstrated fatigue-free in both polarization and energy storage performance and independent bipolar electric fields, which are probably related to the highly dynamic polar nanodomains. More importantly, PLZT thin films also exhibited excellent recoverable energy-storage density and energy efficiency, extracted from the polarization hysteresis loops, making them promising dielectric capacitors for energy-storage applications.     

Enhanced ferroelectric properties of 0.95Pb(Sc0.5Ta0.5)O3–0.05PbTiO3 thin films with Pb(Zr0.52,Ti0.48)O3 seed layer

0.95Pb(Sc_0.5Ta_0.5)O₃–0.05%PbTiO₃ (PSTT5) thin films with and without a Pb(Zr_0.52,Ti_0.48)O₃ (PZT52/48) seed layer were deposited on Pt/Ti/SiO₂/Si(1 0 0) substrates by RF magnetron sputtering. X-ray diffraction patterns indicate that the PSTT5 film with a PZT52/48 seed layer exhibited nearly pure perovskite crystalline phase with highly (4 0 0)-preferred orientation. Piezoresponse force microscopy observations reveal that a large out-of-plane spontaneous polarization exists in the highly (4 0 0)-oriented PSTT5 thin film. The PSTT5/PZT(52/48) possesses good ferroelectric properties with large remnant polarization P_r (12 μC/cm²) and low coercive field E_c (110 kV/cm). Moreover, The perfect butterfly-shaped capacitance–voltage characteristic curve and the relative dielectric constant as high as 733 is obtained in this PSTT5 thin film at 100 kHz.     

Enhancement of the piezoelectric property in PMN-PZT/PZT thin films

0.3Pb(Mg_1/3Nb_2/3)O₃-0.7Pb(Zr_0.52Ti_0.48)O₃/Pb(Zr_0.52Ti_0.48)O₃ (PMN-PZT/PZT) piezoelectric films have been deposited on Pt/Ti/SiO₂/Si substrates via in-situ magnetron sputtering process. The purpose of this work was to investigate heterogeneous interfaces-dependent preferential orientation, micro-morphology, and piezoelectric behaviors of the PMN-PZT/PZT films. Uniform and dense columnar grains are observed by Scanning electron microscope (SEM) analysis as increasing the number of hetero-interfaces. For the film with five heterogeneous interfaces (H5), the superior ferroelectricity (2P_r = 21.6 μC/cm², 2E_c = 60 kV/cm) and dielectricity (ε_r = 1012.1, tanδ = 0.022 at 1 kHz) are obtained, which arises from highly dense columnar grain and the influence of heterogeneous interface strain. Moreover, an excellent piezoelectric constant e₃₁ of 8.2C/m² is achieved in H5 film, which is 3.5 times larger than that of PZT film. It is expected that this study will simulates the design and synthesis of new functional materials, and provides a guidance for actuators device fabrication and applications.     

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.     

Metalorganic chemical vapor deposition of Sr x TiyO z thin films by using mixed metal precursorsO z thin films by using mixed metal precursors

Strontium titanate (Sr _x Ti _y O _z ) thin films were prepared by a chemical vapor deposition method using gaseous compounds, obtained by vaporizing a solid mixture of Sr(dpm)₂ and Ti(O-iPr)₂(dpm)₂ in one step, as the metal sources. The compositions of the films changed in proportion to the ratio of the precursors in the solid mixture, which is contrary to the case of films obtained from a mixture of individual precursor vapors. In the latter case, the film composition was not proportional to the mixing ratio of the precursors. The strontium titanate concentration in the film was changed by the deposition temperature even when the Sr/Ti ratio of the feed was fixed, i.e., the Sr/Ti ratio in the film decreased at high temperatures. An SrTiO₃ film, with an Sr/Ti ratio of 1/1, was obtained at 450 ‡C by using vapors from a solid mixture containing the metal precursors at a Sr/Ti of 1/1. The temperature, 450 ‡C in this case, was lower than that for producing the same film composition by a liquid injection method, 550 ‡C. The decomposition of the Ti and Sr precursors included in the solid mixture and possible reactions between them at elevated temperatures were investigated by thermogravimetry, differential scanning calorimetry, and mass spectrometry. When the solid mixture was heated, the Sr-O bond, that connected Sr to the dpm ligand, was dissociated at temperatures lower than 100 ‡C and the isopropoxide ligand of the Ti precursor was dissociated from the Ti atom at temperatures below 150 ‡C. At 162 ‡C, Ti(O-iPr)₂(dpm)₂ melted, forming an oligomer by reaction with surrounding Ti and Sr precursors. This reaction was confirmed by the presence of a mass peak at m/e=585, corresponding to a hetero-metallic compound containing Sr and Ti. The hetero-metallic compound vaporized at temperatures below 200 ‡C and eventually participated in the formation of a SrTiO₃ film.     

Rapid Microwave Annealing of Amorphous Lead Zirconate Titanate Thin Films Deposited by Sol‐Gel Method on LaNiO3/SiO2/Si Substrates

The heating behavior of LaNiO₃ (LNO) films on SiO₂/Si substrate heated by 2.45 GHz microwave irradiation in the microwave magnetic field was first investigated, and then amorphous Pb(Zr_0.52Ti_0.48)O₃ (PZT) thin films were deposited on LNO‐coated SiO₂/Si substrates by a sol‐gel method and crystallized in the microwave magnetic field. The crystalline phases and microstructures as well as the electrical properties of the PZT films were investigated as a function of the elevated temperature generated by microwave irradiation. The perovskite PZT films with a highly (100)‐preferred orientation can be obtained by microwave annealing at 700°C for only 180 s of total processing time, and have good electrical properties. The results demonstrated that conductive metal oxide LNO as a bottom electrode layer is an advantage for the crystallization of PZT thin films by microwave irradiation in the microwave magnetic field.     

Effect of rapid thermal annealing on the structural and electrical properties of TiO2 thin films prepared by plasma enhanced CVD

Titanium oxide thin films were deposited on p-type Si(100), SiO₂/Si, and Pt/Si substrates by plasma enhanced chemical vapor deposition using high purity Ti(O-i-C₃H₇)₄ and oxygen. As-deposited amorphous TiO₂ thin films were treated by rapid thermal annealing (RTA) in oxygen ambient, and the effects of RTA conditions on the structural and electrical properties of TiO₂ films were studied in terms of crystallinity, microstructure, current leakage, and dielectric constant. The dominant crystalline structures after 600 and 800 ‡C annealing were an anatase phase for the TiO₂ film on SiO₂/Si and a rutile phase for the film on a Pt/Si substrate. The dielectric constant of the as-grown and annealed TiO₂ thin films increased depending on the substrate in the order of Si, SiO₂/Si, and Pt/ Si. The SiO₂ thin layer was effective in preventing the formation of titanium silicide at the interface and current leakage of the film. TEM photographs showed an additional growth of SiO_x from oxygen supplied from both SiO₂ and TiO₂ films when the films were annealed at 1000 ‡C in an oxygen ambient. Intensity analysis of Raman peaks also indicated that optimizing the oxygen concentration and the annealing time is critical for growing a TiO₂ film having high dielectric and low current leakage characteristics.     

Fabrication of Pb(Zr,Ti)O3 thin films utilizing unconventional powder magnetron sputtering (PMS)

Pb(Zr,Ti)O3 (PZT) ferroelectric ceramic films exhibit highly superior ferroelectric, pyroelectric and piezoelectric properties which are promising for a number of applications including non-volatile random access memory devices, non-linear optics, motion and thermal sensors, tunable microwave systems and in energy harvesting (EH) use. In this research, a thin layer of PZT was deposited on two different substrates of Strontium Titanate (STO) and Strontium ruthenate (SRO) by powder magnetron sputtering (PMS) system. The preliminary powders, consisting of PbO, ZrO₂ and TiO_2, were manually mixed and placed into the target holder of the PMS. The deposition was performed at an elevated temperature reaching up to 600 °C via a ceramic heater. This high temperature is required for PZT thin film crystallinity, which is never achieved in conventional physical vapour deposition processes. The phase structure, crystallite size, stress-strain and surface morphology of deposited thin films were characterized using X-ray Diffraction (XRD) and Field Emission Scanning Electron Microscopy (FESEM). The composition of the PZT thin films were also analysed by X-ray photoelectron spectroscopy (XPS). The mechanical properties of the thin films were evaluated with micro-scratch adhesive strength and micro hardness equipment. FESEM results showed that the PZT thin films were successfully deposited on both SRO and STO substrates. The surfaces of the coated samples were free from cracks, relatively smooth, uniform and dense. The profile of X-ray diffraction confirmed the formation of single-c-domain/single crystal perovskite phase grown on both substrates. The XPS analysis have shown that the PZT thin film grown by this method and that a target of PZT+10% PbO is a proper target for growing nominal PZT thin films. The adhesion strength and micro hardness results have confirmed the stability and durability of the thin film on the substrates, although higher values have been reported for thin film of PZT deposited on SRO surfaces.     

Oxygen plasma-assisted ultra-low temperature sol-gel-preparation of the PZT thin films

PbTi_1-xZr_xO₃ (PZT) thin films prepared by sol-gel method have paid much attention due to the excellent performances in piezoelectric, dielectric, ferroelectric and electro-optical. However, the high crystallization temperature of the PZT thin films restricts the compatibility with modern COMS technology. In this work, PbZr_0.52Ti_0.48O₃ (PZT) ferroelectric thin films were successfully prepared by sol-gel method at an ultra-low temperature (～450 °C) in an oxygen plasma-assisted environment. A large spontaneous polarization ～30 μC/cm² and a large dielectric breakdown ～2,900 kV/cm were obtained in the sample annealed at 450 °C for 25 h. We believe that the oxygen plasma-assisted ultra-low temperature (OPAULT) annealing process is a promising way for the sol-gel technology applied in the modern COMS devices.     

The influence of chemical passivation on the PZT/Pt electrode interface

It has been recognized that the interdiffusion of atomic species between a PZT film and the Pt bottom electrode leads to the gradual degradation of a PZT capacitor. In order to prevent this interdiffusion, experimental studies on chemical passivation to the bottom electrode surface were carried out by the sulfurization method. It was observed that a sulfur layer was built up on the Pt substrate with small grains, which resulted in a structural change at the Pt surface. Atomic force microscopy (AFM) showed that the film roughness of the Pt surface was increased by sulfur treatment. Pb(Zr_0.5Ti_0.5)O₃(PZT) thin films were prepared on a Pt/Ti/SiO₂Si bottom electrode by spin-coating techniques. The microstructure and the preferred orientation of the PZT films were shown to depend on the sulfur-treated electrode. The PZT capacitor on a clean Pt electrode was confirmed to be ferroelectric with Pr=17.7 μC/cm² and Ec=65 kV/cm from the P-E hysteresis curves. The fatigue behavior of a PZT film capacitor prepared on a sulfur-treated one was observed to be relaxed, but the absolute value of Pr was paid off.     

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.     

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.     

(SrZrO_3)_(10)(SrTiO_3)_(90)缓冲层对PZT结晶及性能的影响

采用Sol-gel法制备了PbZr0.52Ti0.48O3 (PZT)薄膜,并研究了(SrZrO3)10(SrTiO3)90((SZO)10(STO)90)缓冲层对PZT薄膜结晶和性能的影响.X射线衍射(XRD)结果表明:(SZO)10(STO)90缓冲层对PZT薄膜结晶有取向诱导作用,由(SZO)10(STO)90诱导的PZT薄膜有很强的(111)择优取向,缓冲层将PZT薄膜的取向度α由45.0%提高到了90.1%以上;PZT的(111)择优取向提高了薄膜的电性能,使剩余极化强度Pr从26.8 μC/cm2增大到38.8 μC/cm2.     

High‐energy storage density and excellent temperature stability in antiferroelectric/ferroelectric bilayer thin films

The antiferroelectric/ferroelectric (PbZrO₃/PbZr_0.52Ti_0.48O₃) bilayer thin films were fabricated on a Pt(111)/Ti/SiO₂/Si substrate using sol‐gel method. PbZr_0.52Ti_0.48O₃ layer acts as a buffered layer and template for the crystallization of PbZrO₃ layer. The PbZrO₃ layer with improved quality can share the external voltage due to its smaller dielectric constant and thinner thickness, resulting in the enhancements of electric field strength and energy storage density for the PbZrO₃/PbZr_0.52Ti_0.48O₃ bilayer thin film. The greatly improved electric breakdown strength value of 2615 kV/cm has been obtained, which is more than twice the value of individual PbZr_0.52Ti_0.48O₃ film. The enhanced energy storage density of 28.2 J/cm³ at 2410 kV/cm has been achieved in PbZrO₃/PbZr_0.52Ti_0.48O₃ bilayer film at 20°C, which is higher than that of individual PbZr_0.52Ti_0.48O₃ film (15.6 J/cm³). Meanwhile, the energy storage density and efficiency of PbZrO₃/PbZr_0.52Ti_0.48O₃ bilayer film increase slightly with the increasing temperature from 20°C to 120°C. Our results indicate that the design of antiferroelectric/ferroelectric bilayer films may be an effective way for developing high power energy storage density capacitors with high‐temperature stability.     

Impact of Sr-doping on structural and electrical properties of Pb(Zr0.52Ti0.48)O3 thin films on RuO2 electrodes

In this paper, we investigated the impact of Sr-doping on the structural properties and electrical characteristics of lead zirconate titanate [Pb(Zr_0.52Ti_0.48)O₃, PZT] thin films deposited on RuO₂ electrodes by a sol-gel process and spin-coating technique. We used X-ray diffraction, atomic force microscopy, X-ray photoelectron spectroscopy, and field-emission transmission electron microscopy to explore the structural, morphological, chemical, and microstructural features, respectively, of these films as a function of the growth condition (strontium doping concentrations varied from 1, 3, and 5 mol%). The PZT thin film processed at the 3 mol% Sr exhibited the best electrical characteristics, including a low leakage current of 2.27×10⁻⁷ A/cm² at an electric field of 50 kV/cm, a large capacitance value of 2.74 μF/cm² at a frequency of 10 kHz, and a high remanent polarization of 37.95 μC/cm² at a frequency of 5 kHz. We attribute this behavior to the optimal amount of strontium in the PZT film forming a perovskite structure and a thicker interfacial layer at the PSZT film-RuO₂ electrode interface.     

Tuning electrical properties of PZT film deposited by Pulsed Laser Deposition

The variation of the chemical composition and properties of PZT films as a function of oxygen pressure and laser fluence during pulsed laser deposition is used to tune the electrical properties of the PZT thin films. It is found that the deposition using a 248 nm laser fluence of 1.7 J/cm² and an oxygen pressure of 400 mtorr results the PZT films very similar to that of target material. Changing the laser fluences or oxygen pressure, affects the lead content of the deposited film. In the range of oxygen pressure 50–200 mtorr, the Zr/Zr+Ti and Ti/Zr+Ti ratio varies with oxygen pressure while the Pb/Zr+Ti ratio is almost uniform. Using oxygen pressure as a control parameter to tune the chemical compound and electrical properties of the deposited PZT films, the remnant polarization of the PZT films is tuned in the range of 6.6–42.2 µC/cm², the dielectric constant is controlled in the range of 29–130, and the piezoelectric constant d₃₃ is controlled in the range of 3.82–4.96 pm/V for a 40 nm thick PZT film.     

Residual stress and electrical properties of Pb(Zr0.52,Ti0.48)O3 thin films RF sputtered directly on Cu foils

Polycrystalline Pb(Zr_0.52Ti_0.48)O₃ (PZT) thin films between 250 and 1000 nm thick were deposited on Cu foils via RF magnetron sputtering. Samples were crystallized ex situ between 550°C and 750°C in a low oxygen partial pressure atmosphere, pO₂, in order to avoid oxidation of the substrate. These were compared to films made on more common Pt/TiO_x/SiO₂/Si substrates also crystallized under low pO₂ conditions. The mismatch of the coefficients of thermal expansion for Cu and PZT caused large compressive residual stresses to develop in the films, whereas films on Pt‐Si experienced more moderate tensile stresses. Stress was measured using the sin²ψ method. In addition to mechanical implications, i.e., film cracking and delamination, the effect of residual stress on electrical properties is discussed. Dielectric constants of PZT were lower on Cu than on Pt/TiO_x/SiO₂/Si. This could be due either to a dead layer effect or to the residual stress imposed by the substrate. The remanent polarizations for films on Cu were between 18 and 41 μC/cm², while coercive fields were between 37 and 54kV/cm. Rayleigh analysis was used to describe the role of defects affecting domain wall mobility, as they act as pinning centers and decrease the extrinsic polarization response.